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6,184 results on '"Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP)"'

1. Magnetic expression in kerogen reveals impact on fluid transport

Author

Benjamin Nicot, Jean-Pierre Korb, Isabelle Jolivet, Hervé Vezin, Didier Gourier, Anne-Laure Rollet, Université de Lille, CNRS, TotalEnergies, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX], Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL [ENSCP], 247182|||PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX], PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract

How can the transport of fluids in a confined and complex mixed organic/inorganic matrix be far below the expected value from a topological aspect? A good example of this situation is oil shales. Oil and gas shales are source rocks in which organic matter has matured to form hydrocarbons. They exhibit a dual porous network formed by the intertwining of mineral and organic pores that leads to very low permeability. Still, the exact origin of this extremely low permeability remains somehow unclear. The present communication addresses this important question and provides novel insights on the mechanisms that strongly hinder fluid diffusion in such materials. By combining nuclear and electronic magnetic resonance techniques with SEM imaging, we show evidence that magnetic interaction occurs in kerogen. This results from a magnetic coupling between vanadyl present in porphyrins and the organic matrix. We demonstrate that such coupling retards fluid diffusion and is reversible. This key dynamical feature explains the extremely low mobility of oil in shale rocks. This phenomenon may be a more general feature occurring in several systems where fluids are confined in a complex hierarchical matrix that embeds both organic and inorganic radicals resulting from the aging process.

Published
2022

2. Cathodic control using cellular automata approach

Author

Mariem Zenkri, Dung di Caprio, Fayçal Raouafi, Damien Féron, Laboratoire de Physicochimie des Matériaux - IPEST(La Marsa, Tunisia), Institut préparatoire aux études scientifiques et techniques [La Marsa] (IPEST), Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Faculté des Sciences de Bizerte [Université de Carthage], Université de Carthage - University of Carthage, Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Service de la Corrosion et du Comportement des Matériaux dans leur Environnement (SCCME), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay

Subjects
corrosion, cellular automata, Mechanical Engineering, Metals and Alloys, General Medicine, cathodic control, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Mechanics of Materials, dissolved oxygen, Materials Chemistry, Environmental Chemistry, passivation, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat]
Abstract

International audience; We present a stochastic three dimensional cellular automata model of aqueous corrosion. We consider the cathodic reaction with dissolved oxygen and different concentrations of the oxidizer. We study the role and the stability of the passive layer and its effect on the kinetics, surface morphology and roughness of the metallic surface. The model considers balanced spatially separated anodic and cathodic reactions and is capable of illustrating the cathodic control of the corrosion rate. Besides the electrochemical reactions, we take into account ionic diffusion, acido/basic neutralization. Results are compared to aqueous corrosion of Fe in near neutral solution.

Published
2022

3. PEPR TASE: Technologies avancées des systèmes energétiques

Author

Guillemoles, Jean-François, Azais, Philipe, Retiere, Nicolas, Institut de Recherche et Développement sur l'Energie Photovoltaïque (IRDEP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-EDF R&D (EDF R&D), EDF (EDF)-EDF (EDF), Institut Photovoltaïque d’Ile-de-France (IPVF), 91120 Palaiseau, France (IPVF), École polytechnique (X)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire de Génie Electrique de Grenoble (G2ELab ), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)

Subjects
[SPI]Engineering Sciences [physics], [SDE]Environmental Sciences, [CHIM]Chemical Sciences, [SHS]Humanities and Social Sciences
Abstract

International audience; Programme d'augmentation de la part des énergies renouvelables dans le mix réseau(Plan Pluriannuel de l'Energie : PPE)• Installations massives d'EnR : de 48,6 GWc fin 2017 à 100 -110 GWc en 2028• PV : 35 à 44 GWc, Eolien : ~ 33 - 35 GWc, dont 5 à 6 GWc en mer, hydro. ~26,5 GWp• connectés au réseau (36 % de l'électricité fournie par ENR).• Développer les infrastructures de recharge des véhicules électriques, l'écrêtement des pointes etl'autoconsommation, la flexibilité et la résilience des réseaux• En 2050: besoin en énergie finale ~1 060 TWh (1 628 TWh en 2018), dont ~580 TWh électriquesOpérer une transition responsable• Qui mette l’humain au centre , qui soit bien appropriée socialement;• Qui soit conforme au développement durable et minimise les impacts environnementaux;Plan de réindustrialisation et de souveraineté (France Relance)• Moderniser l’appareil productif et décarboner l'industrie ;• (Re)localiser les activités stratégiques critiques ;• Innover, en soutenant les investissements en R&D tout en développant les compétences.

Published
2023

4. Deconvoluting the benefits of porosity distribution in layered electrodes on the electrochemical performance of Li-ion batteries

Author

Abbos Shodiev, Mehdi Chouchane, Miran Gaberscek, Oier Arcelus, Jiahui Xu, Hassan Oularbi, Jia Yu, Jianlin Li, Mathieu Morcrette, Alejandro A. Franco, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratory for Materials Electrochemistry, National Institute of Chemistry, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Northeast Agricultural University [Harbin], Beijing Municipal Bureau of Land and Resources [Beijing], Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )

Subjects
Renewable Energy, Sustainability and the Environment, Energy Engineering and Power Technology, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract

International audience; Thick Lithium Ion Battery (LIB) electrodes suffer from poor rate capability and high ionic impedance due to their thickness and mesostructure. Therefore, optimizing thick electrode architectures becomes crucial. In this work, we report a systematic assessment of the ionic resistance in heterogeneous porous electrodes through the combination of computational simulations using a 4D-resolved model and experimental measurements. The first part of the study is devoted to a general assessment of Electrochemical Impedance Spectroscopy (EIS) spectra, mapping the impact of ionic and electronic resistances on the overall impedances of uncalendered and calendered LiNi1/3Mn1/3Co1/3O2, LiFePO4 and graphite electrodes. In the second part, in silico-generated electrodes with different porosities are used in computational EIS simulations to analyze the impact of the electrode porosity on the ionic impedance. As expected, the results show that a lower porosity leads to a higher ionic impedance because of a higher electrode tortuosity factor. Furthermore, in silico-generated electrodes with different porosities were stacked and assembled to create heterogeneities of porosity along the thickness, and used in computational EIS and galvanostatic discharge simulations. The computational results show that the porosity heterogeneity along the electrode thickness has a significant effect on the ionic impedance and capacity of the electrode. The electrode architecture with progressively decreasing porosity from separator to current collector shows the highest performance, a trend validated by our in house experimental EIS and galvanostatic discharge also reported in this manuscript. Overall, we conclude that the ionic resistance in a thick electrode can be effectively reduced through proper tuning of the porosity heterogeneity. The proposed heterogeneous electrode architectures presented here could enormously help building efficient thick electrodes for LIBs.

Published
2022

5. CADPS functional mutations in patients with bipolar disorder increase the sensitivity to stress

Author

Jérémy Sitbon, Dennis Nestvogel, Caroline Kappeler, Aude Nicolas, Stephanie Maciuba, Annabelle Henrion, Réjane Troudet, Elisa Courtois, Gaël Grannec, Violaine Latapie, Caroline Barau, Philippe Le Corvoisier, Nicolas Pietrancosta, Chantal Henry, Marion Leboyer, Bruno Etain, Marika Nosten-Bertrand, Thomas F. J. Martin, JeongSeop Rhee, Stéphane Jamain, Institut Mondor de Recherche Biomédicale (IMRB), Institut National de la Santé et de la Recherche Médicale (INSERM)-IFR10-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), Fondation FondaMental [Créteil], Max Planck Institute of Experimental Medicine [Göttingen] (MPI), Max-Planck-Gesellschaft, University of Wisconsin-Madison, Institut du Fer à Moulin (IFM - Inserm U1270 - SU), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU), Plateforme de Ressources Biologiques [Henri Mondor AP-HP, Créteil] (PRB), Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-CHU Henri Mondor, Centre d'Investigation Clinique Henri Mondor (CIC Henri Mondor), Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Hôpital Henri Mondor-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Groupe Henri Mondor-Albert Chenevier, Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Hôpital Henri Mondor-Hôpital Albert Chenevier, Hôpitaux Universitaire Saint-Louis, Lariboisière, Fernand-Widal, Université Sorbonne Paris Cité (USPC), Optimisation thérapeutique en Neuropsychopharmacologie (OPTeN (UMR_S_1144 / U1144)), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Paris Cité (UPCité), IMRB - 'Neuropsychiatrie translationnelle' [Créteil] (U955 Inserm - UPEC), Institut National de la Santé et de la Recherche Médicale (INSERM)-IFR10-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut National de la Santé et de la Recherche Médicale (INSERM)-IFR10-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), IMRB - 'NeuroPsychologie Interventionnelle' [Créteil] (U955 Inserm - UPEC), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Systèmes glutamatergiques normaux et pathologiques = Normal and Pathologic Glutamatergic Neurons (NPS), Neuroscience Paris Seine (NPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Analyse, Interactions Moléculaires et Cellulaires (LBM-E2), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Jamain, Stéphane

Subjects
Bipolar Disorder, Neuronal Plasticity, [SDV.NEU.NB]Life Sciences [q-bio]/Neurons and Cognition [q-bio.NC]/Neurobiology, [SDV.MHEP.PSM] Life Sciences [q-bio]/Human health and pathology/Psychiatrics and mental health, Calcium-Binding Proteins, [SDV.NEU.NB] Life Sciences [q-bio]/Neurons and Cognition [q-bio.NC]/Neurobiology, Vesicular Transport Proteins, Nerve Tissue Proteins, [SDV.GEN.GH] Life Sciences [q-bio]/Genetics/Human genetics, Exocytosis, Mice, Cellular and Molecular Neuroscience, Psychiatry and Mental health, [SDV.GEN.GH]Life Sciences [q-bio]/Genetics/Human genetics, [SDV.MHEP.PSM]Life Sciences [q-bio]/Human health and pathology/Psychiatrics and mental health, Mutation, Animals, Humans, Calcium, Molecular Biology
Abstract

International audience; Bipolar disorder is a severe and chronic psychiatric disease resulting from a combination of genetic and environmental risk factors. Here, we identified a significant higher mutation rate in a gene encoding the calcium-dependent activator protein for secretion (CADPS) in 132 individuals with bipolar disorder, when compared to 184 unaffected controls or to 21,070 non-psychiatric and non-Finnish European subjects from the Exome Aggregation Consortium. We found that most of these variants resulted either in a lower abundance or a partial impairment in one of the basic functions of CADPS in regulating neuronal exocytosis, synaptic plasticity and vesicular transporter-dependent uptake of catecholamines. Heterozygous mutant mice for Cadps+/- revealed that a decreased level of CADPS leads to manic-like behaviours, changes in BDNF level and a hypersensitivity to stress. This was consistent with more childhood trauma reported in families with mutation in CADPS, and more specifically in mutated individuals. Furthermore, hyperactivity observed in mutant animals was rescued by the mood-stabilizing drug lithium. Overall, our results suggest that dysfunction in calcium-dependent vesicular exocytosis may increase the sensitivity to environmental stressors enhancing the risk of developing bipolar disorder.

Published
2022

6. Identification of bacterial lipo-amino acids: origin of regenerated fatty acid carboxylate from dissociation of lipo-glutamate anion

Author

Amandine Hueber, Yves Gimbert, Geoffrey Langevin, Jean-Marie Galano, Alexandre Guy, Thierry Durand, Nicolas Cenac, Justine Bertrand-Michel, Jean-Claude Tabet, Gestionnaire, HAL Sorbonne Université 5, MetaboHUB-MetaToul, Génopole Toulouse Midi-Pyrénées [Auzeville] (GENOTOUL), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Vétérinaire de Toulouse (ENVT), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut de Recherche en Santé Digestive (IRSD ), Institut des Maladies Métaboliques et Casdiovasculaires (UPS/Inserm U1297 - I2MC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Inserm, PhD Grant, Région Occitanie, PhD Grant, MetaToul-MetaboHUB, Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Anions, Spectrometry, Mass, Electrospray Ionization, Tandem mass spectrometry, Lipidomic, Ion-dipole Abbreviations ACN Acetonitrile CID Collision-induced dissociation DCM Dichloromethane DFT Density functional theory EcN Escherichia coli ESI Electrospray, Fatty Acids, Organic Chemistry, Clinical Biochemistry, Lipoamino acid, Glutamic Acid, Biochemistry, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Humans, Regeneration, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Amino Acids
Abstract

The identification of bacterial metabolites produced by the microbiota is a key point to understand its role in human health. Among them, lipo-amino acids (LpAA), which are able to cross the epithelial barrier and to act on the host, are poorly identified. Structural elucidation of few of them was performed by high-resolution tandem mass spectrometry based on electrospray combined with selective ion dissociations reach by collision-induced dissociation (CID). The negative ions were used for their advantages of yielding only few fragment ions sufficient to specify each part of LpAA with sensitivity. To find specific processes that help structural assignment, the negative ion dissociations have been scrutinized for an LpAA: the N-palmitoyl acyl group linked to glutamic acid (C16Glu). The singular behavior of [C16Glu-H]¯ towards CID showed tenth product ions, eight were described by expected fragment ions. In contrast, instead of the expected product ions due to CONH-CH bond cleavage, an abundant complementary dehydrated glutamic acid and fatty acid anion pair were observed. Specific to glutamic moiety, they were formed by a stepwise dissociation via molecular isomerization through ion–dipole formation prior to dissociation. This complex dissociated by partner splitting either directly or after inter-partner proton transfer. By this pathway, surprising regeneration of deprotonated fatty acid takes place. Such regeneration is comparable to that occurred from dissociation to peptides containing acid amino-acid. Modeling allow to confirm the proposed mechanisms explaining the unexpected behavior of this glutamate conjugate.

Published
2022

7. Composite Mn–Co electrode materials for supercapacitors: why the precursor's morphology matters!

Author

Ronan Invernizzi, Alexia Lemoine, Lénaïc Madec, François Weill, Marie-Anne Dourges, Céline Tang, Domitille Giaume, Isabelle Baraille, Pierre Louis Taberna, Delphine Flahaut, Jacob Olchowka, Liliane Guerlou-Demourgues, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The authors would like to thank AID as well as Bordeaux INP for financial support (PhD funding and research fees). The authors thank also Région Nouvelle Aquitaine and the French National Research Agency (STORE-EX Labex Project ANR-10-LABX-76-01) for financial support and fruitful discussions., and ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010)

Subjects
General Engineering, General Materials Science, Bioengineering, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Atomic and Molecular Physics, and Optics
Abstract

International audience; In the energy storage field, an electrode material must possess both good ionic and electronic conductivities to perform well, especially when high power is needed. In this context, the development of composite electrode materials combining an electrochemically active and good ionic conductor phase with an electronic conductor appears as a perfectly adapted approach to generate a synergetic effect and optimize the energy storage performance. In this work, three layered MnO2 phases with various morphologies (veals, nanoplatelets and microplatelets) were associated with electronic conductor cobalt oxyhydroxides with different platelet sizes (~20 nm vs 70 nm wide), to synthesize 6 different composites by exfoliation and restacking process. The influence of precursors’ morphology on the distribution between the Mn and Co objects within the composites was carefully investigated and correlated to the electrochemical performance of the final restacked material. Overall, the best performing restacked composite was obtained by combining MnO2 possessing a veal morphology with the smallest cobalt oxyhydroxide nanoplatelets, leading to the most homogeneous distribution of the Mn and Co objects at the nanoscale. More generally, the aim of this work is to understand how the size and morphology of the precursors building blocks influence their distribution homogeneity within the final composite and to find the most compatible building blocks to reach a homogenous distribution at nanoscale.

Published
2022

8. The Ir–OOOO–Ir transition state and the mechanism of the oxygen evolution reaction on IrO2(110)

Author

Tobias Binninger, Marie-Liesse Doublet, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )

Subjects
Nuclear Energy and Engineering, Renewable Energy, Sustainability and the Environment, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Environmental Chemistry, Pollution
Abstract

International audience; Carefully assessing the energetics along the pathway of the oxygen evolution reaction (OER), our computational study reveals that the "classical" OER mechanism on the (110) surface of iridium dioxide (IrO 2) must be reconsidered. We find that the OER follows a bi-nuclear mechanism with adjacent top surface oxygen atoms as fixed adsorption sites, whereas the iridium atoms underneath play an indirect role and maintain their saturated 6-fold oxygen coordination at all stages of the reaction. The oxygen molecule is formed, via an Ir-OOOO-Ir transition state, by association of the outer oxygen atoms of two adjacent Ir-OO surface entities, leaving two intact Ir-O entities at the surface behind. This is drastically different from the commonly considered mono-nuclear mechanism where the O 2 molecule evolves by splitting of the Ir-O bond in an Ir-OO entity. We regard the rather weak reducibility of crystalline IrO 2 as the reason for favoring the novel pathway, which allows the Ir-O bonds to remain stable and explains the outstanding stability of IrO 2 under OER conditions. The establishment of surface oxygen atoms as fixed electrocatalytically active sites on a transitionmetal oxide represents a paradigm shift for the understanding of water oxidation electrocatalysis, and it reconciles the theoretical understanding of the OER mechanism on iridium oxide with recently reported experimental results from operando X-ray spectroscopy. The novel mechanism provides an efficient OER pathway on a weakly reducible oxide, defining a new strategy towards the design of advanced OER catalysts with combined activity and stability.

Published
2022

9. Controlling the interfacial reactions and environment of rare-earth ions in thin oxide films towards wafer-scalable quantum technologies

Author

Philippe Goldner, Christophe Labbé, Alexandre Tallaire, Philippe Marcus, Alban Ferrier, Nao Harada, Antoine Seyeux, Diana Serrano, Xavier Portier, Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU), Nanomatériaux, Ions et Métamatériaux pour la Photonique (NIMPH), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)

Subjects
Materials science, Silicon, rare earth, thin film, Oxide, chemistry.chemical_element, 02 engineering and technology, Substrate (electronics), 01 natural sciences, [SPI.MAT]Engineering Sciences [physics]/Materials, [PHYS.PHYS.PHYS-COMP-PH]Physics [physics]/Physics [physics]/Computational Physics [physics.comp-ph], Condensed Matter::Materials Science, chemistry.chemical_compound, Laser linewidth, 0103 physical sciences, General Materials Science, Wafer, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, Thin film, 010306 general physics, quantum technologies, [PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics], business.industry, square, Doping, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, [SPI.ELEC]Engineering Sciences [physics]/Electromagnetism, chemistry, Chemistry (miscellaneous), [SPI.OPTI]Engineering Sciences [physics]/Optics / Photonic, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Optoelectronics, Photonics, 0210 nano-technology, business
Abstract

Rare earth (RE) doped oxides have demonstrated great potential for photonic applications and have also appeared as promising candidates for quantum memory devices and microwave to optical transducers. Here, we investigate the potential of Chemical Vapor Deposited (CVD) europium-doped Y2O3thin films on silicon as a new platform for integrated quantum devices. We aim at improving the optical properties of such thin films by carefully controlling the RE ion's environment. In particular, we study the effect of annealing post treatments and demonstrate that a significant source of broadening of the optical transition arises from interfacial reactions with the silicon substrate. We thus propose to encapsulate RE ions between undoped high-quality thick layers in order to limit the impact of interfacial reactions on their properties during thermal annealing. Using this approach, we succeeded in measuring a narrow inhomogeneous linewidth of 18 GHz and an ultra-narrow homogeneous linewidth of 5 MHz inferred from spectral hole width. These results are promising towards the use of these engineered RE doped thin films for the development of a scalable nanostructured spin-photon interface. In addition, our strategy could be applied to a large variety of oxide films for a broad range of applications. Paper published in Materials Advances.

Published
2022

10. Ordering of a nanoconfined water network around zinc Ions induces high proton conductivity in layered titanate

Author

Seongkoo Kang, Kyle G. Reeves, Ivette Aguilar, Ana Gabriela Porras Gutierrez, Jean-Claude Badot, Serge Durand-Vidal, Christophe Legein, Monique Body, Antonella Iadecola, Olaf J. Borkiewicz, Olivier Dubrunfaut, Franck Fayon, Pierre Florian, Damien Dambournet, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Argonne National Laboratory [Lemont] (ANL), Laboratoire Génie électrique et électronique de Paris (GeePs), CentraleSupélec-Sorbonne Université (SU)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), and Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
General Chemical Engineering, Materials Chemistry, [CHIM]Chemical Sciences, General Chemistry
Abstract

International audience; We demonstrated that the chemical intercalation of Zn$^{2+}$ ions within the interlayer space of the structure of a disordered layered titanate results in a drastic increase of the room temperature bulk proton conductivity from 8.11 x 10$^{-5}$ S.m$^{-1}$ for the pristine to 3.7 x10$^{-2}$ S.m-1 for Zn-titanate. Because of the crystallographic disordered nature of these compounds, we combined different techniques to establish the structural-transport relationships. Pair distribution function revealed that upon chemical insertion of Zn$^{2+}$ , the local lepidocrocite arrangement is maintained, providing a suited model to investigate the effect of chemically intercalated ions on the transport properties and dynamics within the interlayer space. Broadband dielectric spectroscopy (50 to 10$^{10}$ Hz) enabled to establish that Zn$^{2+}$ inclusion promotes proton-hopping by self-dissociation of H$_2$O molecules yielding high proton mobility. Using Zn-K edge EXAFS and chemical analyses (EDX, TGA, $^1$H NMR), Zn$^{2+}$ ions were shown to be stabilized by ZnCl$_2$ (H$_2$O) complex within the interlayer space. Such complexes induce an increase of the H-bonding strength as evidenced by $^1$H NMR, yielding a fast proton motion. Molecular dynamic simulations highlighted proton transfer between water molecules from structural interlayer and bonded to Zn 2+ ions. The increasing interactions between these water molecules favors proton transfer at the origin of the fast bulk proton conductivity, which was assigned to a Grotthuss-type mechanism taking place at long-range order. This work provides a better understanding of how ion-water interactions mediated ionic transport and opens perspectives into the design of ionic conductors that can be used in energy storage applications.

Published
2023

11. Chemical Design of IrS2 Polymorphs to Understand the Charge/Discharge Asymmetry in Anionic Redox Systems

Author

Thomas Marchandier, Sathiya Mariyappan, Artem M. Abakumov, Stéphane Jobic, Bernard Humbert, Jean-Yves Mevellec, Gwenaëlle Rousse, Maxim Avdeev, Rémi Dedryvère, Dominique Foix, Antonella Iadecola, Marie-Liesse Doublet, Jean-Marie Tarascon, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Skolkovo Institute of Science and Technology [Moscow] (Skoltech), Institut des Matériaux Jean Rouxel (IMN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - Ecole Polytechnique de l'Université de Nantes (Nantes Univ - EPUN), Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), The University of Sydney, Australian Nuclear Science and Technology Organisation [Australie] (ANSTO), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Collège de France - Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), U.S. Department of Energy under contract no. DE-AC02-06CH11357European Research Council (ERC) (FP/2014)/ERC grant/project no. 670116-ARPEMA, ANR-10-EQPX-0045,ROCK,Spectromètre EXAFS Rapide pour Cinétiques Chimiques(2010), Chaire Chimie du solide et énergie, Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Sorbonne Université (SU)

Subjects
General Chemical Engineering, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Materials Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, [CHIM.OTHE]Chemical Sciences/Other, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, 0104 chemical sciences
Abstract

International audience; Li-ion batteries are growing in demand and such growth calls for the quest for high-energy-density electrode materials. Li-rich layered oxides that show both cationic and anionic redox are expected to meet the high energy requirement. However, the oxygen anion activity triggers numerous structural and electronic rearrangements that need to be understood prior to envisioning applications. Here, we chemically design two new LixIrS2 polymorphs to further interrogate the mechanisms of the ligand redox process. By combined structural and spectroscopic characterizations, we show that electrochemical lithiation/delithiation of the polymorphs involve different sulfur redox couples that stand as unusual behavior. These structure-dependent kinetic pathways lead to an similar to 1 V difference between the two polymorphs, hence providing the missing link between the structure and hysteresis in anionic redox systems. These insights into the origin of hysteresis can guide proper parameters to cure it, hence laying the groundwork for the design of new practical electrode materials.

Published
2021

12. Exciton spectroscopy and unidirectional transport in MoSe2-WSe2 lateral heterostructures encapsulated in hexagonal boron nitride

Author

Dorian Beret, Ioannis Paradisanos, Hassan Lamsaadi, Ziyang Gan, Emad Najafidehaghani, Antony George, Tibor Lehnert, Johannes Biskupek, Ute Kaiser, Shivangi Shree, Ana Estrada-Real, Delphine Lagarde, Xavier Marie, Pierre Renucci, Kenji Watanabe, Takashi Taniguchi, Sébastien Weber, Vincent Paillard, Laurent Lombez, Jean-Marie Poumirol, Andrey Turchanin, Bernhard Urbaszek, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre d'élaboration de matériaux et d'études structurales (CEMES), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Friedrich-Schiller-Universität = Friedrich Schiller University Jena [Jena, Germany], Universität Ulm - Ulm University [Ulm, Allemagne], University of Washington [Seattle], Équipe Matériaux et Procédés pour la Nanoélectronique (LAAS-MPN), Laboratoire d'analyse et d'architecture des systèmes (LAAS), Université Toulouse Capitole (UT Capitole), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université Toulouse - Jean Jaurès (UT2J), Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université Toulouse Capitole (UT Capitole), Université de Toulouse (UT), Technische Universität Darmstadt - Technical University of Darmstadt (TU Darmstadt), National Institute for Materials Science (NIMS), Institut Photovoltaïque d’Ile-de-France (UMR) (IPVF), École polytechnique (X)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-TOTAL FINA ELF-EDF (EDF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Photovoltaïque d’Ile-de-France (ITE) (IPVF)-Air Liquide [Siège Social], Institut Photovoltaïque d’Ile-de-France (ITE) (IPVF), Institut de Recherche et Développement sur l'Energie Photovoltaïque (IRDEP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-EDF R&D (EDF R&D), EDF (EDF)-EDF (EDF), ANR-17-EURE-0009,NanoX,Science et Ingénierie à l'Echelle Nano(2017), and European Project: 619318,EC:FP7:ICT,FP7-ICT-2013-11,FLAG-ERA(2013)

Subjects
Two-dimensional, Mechanics of Materials, Mechanical Engineering, General Materials Science, ddc:500, General Chemistry, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], NATURAL sciences & mathematics, Condensed Matter Physics, Two-dimensional materials, materials
Abstract

Chemical vapor deposition (CVD) allows lateral edge epitaxy of transition metal dichalcogenide heterostructures. Critical for carrier and exciton transport is the material quality and the nature of the lateral heterojunction. Important details of the optical properties were inaccessible in as-grown heterostructure samples due to large inhomogeneous broadening of the optical transitions. Here we perform optical spectroscopy of CVD grown MoSe2-WSe2 lateral heterostructures, encapsulated in hBN. Photoluminescence (PL), reflectance contrast and Raman spectroscopy reveal optical transition linewidths similar to high quality exfoliated monolayers, while PL imaging experiments uncover the effective excitonic diffusion length of both materials. The typical extent of the covalently bonded MoSe2-WSe2 heterojunctions is 3 nm measured by scanning transmission electron microscopy (STEM). Tip-enhanced, sub-wavelength optical spectroscopy mapping shows the high quality of the heterojunction which acts as an excitonic diode resulting in unidirectional exciton transfer from WSe2 to MoSe2.

Published
2022

13. Bottom-Up Design of Configurable Oligomer-Derived Conducting Metallopolymers for High-Power Electrochemical Energy Storage

Author

Evgeniya Vorobyeva, Mathieu Salanne, Maria R. Lukatskaya, Franziska Lissel, Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Leibniz-Institut für Polymerforschung Dresden e.V. (IPF), Leibniz Association, Technische Universität Dresden = Dresden University of Technology (TU Dresden), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Battery (electricity), Materials science, Metal ions in aqueous solution, Supramolecular chemistry, General Physics and Astronomy, chemistry.chemical_element, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Oligomer, Metal, [SPI]Engineering Sciences [physics], chemistry.chemical_compound, conjugated oligomers, Side chain, General Materials Science, Electrical conductor, supercapacitors, electrochemical energy storage, General Engineering, 021001 nanoscience & nanotechnology, conductive metallopolymers, 0104 chemical sciences, chemistry, visual_art, visual_art.visual_art_medium, Lithium, 0210 nano-technology
Abstract

International audience; In this Perspective, we sketch out a vision of fast charging and self-healable energy systems that are primarily organic, feature only abundant elements, and operate with ions other than lithium. Using conductive oligomers as highly configurable building blocks, it is possible to create intrinsically adaptable conductive polymeric networks that can be rejuvenated and recycled using simple and safe chemical treatments. Using the versatile organic chemistry toolbox, these oligomers can be further functionalized, for example, with redox-active side chains for high charge storage capacity and ligands capable of complexing metal centers. Cross-linking with metal ions converts the soluble oligomers into insoluble supramolecular networks to yield high-performing electrode materials. The oligomer-based approach can thus provide an exceptional level of control to the design of organic-based battery materials.

Published
2021

14. Stacking Versatility in Alkali-Mixed Honeycomb Layered NaKNi2TeO6

Author

Gwenaëlle Rousse, François Weill, François Fauth, Montse Casas-Cabanas, Jon Serrano-Sevillano, Marie-Liesse Doublet, Romain Berthelot, Bernard Fraisse, Dany Carlier, Danielle Laurencin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), CIC ENERGIGUNE - Parque Tecnol Alava, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CELLS ALBA, Barcelona 08290, Spain, Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ikerbasque - Basque Foundation for Science, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), The BL04-MSPD staff of CELLS-ALBA synchrotron is acknowledged for granting beamtime through InHouse quota (proposal 2020014011)., Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Basque Foundation for Science (Ikerbasque)

Subjects
Diffraction, Chemistry, Sodium, Stacking, Honeycomb (geometry), Oxides, Context (language use), [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 021001 nanoscience & nanotechnology, Alkali metal, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Chemical physics, Cations, Potassium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, Physical and Theoretical Chemistry, Layers, 0210 nano-technology, Stacking fault
Abstract

International audience; The reaction between P2-type honeycomb layered oxides Na2Ni2TeO6 and K2Ni2TeO6 enables the formation of NaKNi2TeO6. The compound is characterized by X-ray diffraction and 23Na solid-state nuclear magnetic resonance spectroscopy, and the structure is discussed through density functional theory calculations. In addition to the honeycomb Ni/Te cationic ordering, NaKNi2TeO6 exhibits a unique example of alternation of sodium and potassium layers instead of a random alkali-mixed occupancy. Stacking fault simulations underline the impact of the successive position of the Ni/Te honeycomb layers and validate the presence of multiple stacking sequences within the powder material, in proportions that evolve with the synthesis conditions. In a broader context, this work contributes to a better understanding of the alkali-mixed layered compounds.

Published
2021

15. The formulation of a CMC binder/silicon composite anode for Li-ion batteries: from molecular effects of ball milling on polymer chains to consequences on electrochemical performances

Author

Mariama Ndour, Jean-Pierre Bonnet, Sébastien Cavalaglio, Tristan Lombard, Matthieu Courty, Luc Aymard, Cédric Przybylski, Véronique Bonnet, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Laboratoire des technologies de la microélectronique (LTM ), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
Chemistry (miscellaneous), [CHIM]Chemical Sciences, General Materials Science
Abstract

The semi-synthetic polysaccharide carboxymethylcellulose (CMC) is one of the most studied and effective polymer binders for silicon-based anodes in Li-ion batteries.

Published
2022

16. Challenges and Methods for the Study of CPP Translocation Mechanisms

Author

Astrid Walrant, Nicolas Rodriguez, Françoise Illien, Sandrine Sagan, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
chemistry.chemical_classification, 0303 health sciences, Bilayer, [SDV]Life Sciences [q-bio], Peptide, Biological membrane, 02 engineering and technology, 021001 nanoscience & nanotechnology, Fluorescence, Fluorescence spectroscopy, Cell membrane, 03 medical and health sciences, Membrane, medicine.anatomical_structure, chemistry, Biophysics, medicine, 0210 nano-technology, Tropism, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology
Abstract

Fluorescence-based methods are widely used to detect crossing of peptides across model or biological membranes. For membrane-active peptides, i.e., peptides that have strong membrane tropism, fluorescence experiments must be accompanied by relevant controls, otherwise they can lead to inconsistent interpretation and underestimation of their limitations. Here we describe how to prepare samples to study fluorescent peptide crossing droplet interface bilayer (model membrane) or cell membrane (biological membrane) and the pitfalls that can affect observational qualitative and quantitative data.

Published
2022

17. Is There a Ready-Recipe for Hard Carbon-Electrode Engineering to Enhance Na-Ion Battery Performance?

Author

Joanna Conder, Claire Villevieille, Jean-Marc Le Meins, Camélia Matei Ghimbeu, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI), Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), European Project: 646433,H2020,H2020-LCE-2014-3,NAIADES(2015), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )

Subjects
anodes, Energy Engineering and Power Technology, lignin, [CHIM.MATE]Chemical Sciences/Material chemistry, chitin, cellulose, Materials Chemistry, Electrochemistry, Chemical Engineering (miscellaneous), sodium ion batteries, [CHIM]Chemical Sciences, Electrical and Electronic Engineering, chitosan, hard carbon
Abstract

International audience; Hard carbon (HC) materials are commonly used as anode materials in Na-ion batteries. In most of the cases, their electrochemical performance is correlated only to their physicochemical properties, and the impact of the electrode additives (binders–conductive agent) and electrolyte is often neglected. In this work, a systematic study is performed to understand the role of electrode/electrolyte engineering on HC initial Coulombic efficiency (iCE), specific capacity, and cycle stability. Four HCs obtained by pyrolysis of several biopolymers, i.e., cellulose (HC-Cell), chitosan (HC-Chs), chitin (HC-Cht), and lignin (HC-Lig), are used. The binder was found to have an important impact on the electrochemical performance, with PVDF resulting in better performance than CMC. The carbon black additive had no significant impact on CMC-based electrochemical performance while it boosted the electrochemical performance of PVDF-based electrodes. For an optimized formulation (PVDF/carbon black), the best HC performance in NaPF6 in 1 EC:DEC was delivered by HC-Cell (83% iCE, 332 mAh g–1 at C/10, and 97% retention). This was attributed to its large graphene interlayer space, high purity, and low surface area. HC-Cht and HC-Chs exhibited similar good electrochemical performance (∼280 mAh g–1) whereas the use of HC-Lig resulted in low iCE and capacity fading overcycling due to the high level of impurities in its structure. This could be overcome by changing the electrolyte salt, by using NaClO4 (76% retention) instead of NaPF6 (52% retention). Based on the obtained results, the electrochemical performance could be correlated with the HC physicochemical properties and binder/conductive additive. It could be demonstrated that careful electrode engineering combined with proper electrolyte selection and tuned HC properties allowed all investigated materials achieving reasonable iCE (up to 83%), high specific capacity (∼280 to 332 mAh g–1), and high-capacity retention (72–97% after 50 cycles).

Published
2022

18. High-Field NMR, Reactivity, and DFT Modeling Reveal the γ-Al2O3 Surface Hydroxyl Network

Author

Nicolas Merle, Tarnuma Tabassum, Susannah L. Scott, Alessandro Motta, Kai Szeto, Mostafa Taoufik, Régis Michaël Gauvin, Laurent Delevoye, Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181, UCCS Équipe Catalyse et synthèse éco-compatible, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL [ENSCP], UCCS Équipe RMN et matériaux inorganiques, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC)

Subjects
General Medicine, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Catalysis, Alumina, Density Functional Calculations, Solid-State NMR, Surface Chemistry
Abstract

Aluminas are strategic materials used in many major industrial processes, either as catalyst supports or as catalysts in their own right. The transition alumina γ-Al2O3 is a privileged support, whose reactivity can be tuned by thermal activation. This study provides a qualitative and quantitative assessment of the hydroxyl groups present on the surface of γ-Al2O3 at three different dehydroxylation temperatures. The principal [AlOH] configurations are identified and described in unprecedented detail at the molecular level. The structures were established by combining information from high-field 1H and 27Al solid-state NMR, IR spectroscopy and DFT calculations, as well as selective reactivity studies. Finally, the relationship between the hydroxyl structures and the molecular-level structures of the active sites in catalytic alkane metathesis is discussed. 61;37

Published
2022

19. Probing the Electrochemical Li Insertion–Extraction Mechanism in Sputtered LiNi0.5Mn1.5O4 Thin Film Cathode for Li‐Ion Microbattery

Author

Ankush Bhatia, Clement Leviel, Maxime Hallot, Jean‐Pierre Pereira‐Ramos, Christophe Lethien, Pascal Roussel, Rita Baddour‐Hadjean, Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Circuits Systèmes Applications des Micro-ondes - IEMN (CSAM - IEMN ), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), The authors thank the French ANR within the CASSIOPES project (ANR-17-CE09-0016-01) for financial support. The French network on electrochemical energy storage (RS2E) and the Store-Ex Labex are also thanked for their support. The French RENATECH network is greatly acknowledged for the use of microfabrication facilities. Chevreul Institute (FR 2638), Ministère de l’Enseignement Supérieur et de la Recherche, Région Hauts de France, and FEDER are acknowledged for supporting and funding XRD facilities., RS2E, Renatech Network, CMNF, ANR-17-CE09-0016,CASSIOPES,Caractérisations AvancéeS in SItu / OPerando de micro-batteriES 3D tout solide à ions lithium développées en technologie couche mince ALD(2017), ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )

Subjects
Mechanics of Materials, Mechanical Engineering, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.OTHE]Chemical Sciences/Other
Abstract

International audience; Due to its great theoretical capacity (147 mAh g−1) and high operating potential (4.7 V vs Li+/Li), Co-free spinel LiNi0.5Mn1.5O4 (LNMO) is one of the most promising thin film cathodes allowing designing Li-ion micro-batteries with a high specific energy. In this work, the Li extraction–insertion mechanism in sputtered LNMO thin films is investigated by X-ray diffraction and Raman spectroscopy during the first electrochemical cycle. A one-step phase transition involving two cubic phases is revealed, consisting of a wide solid solution region (0.3 ≤ x ≤ 1 in LixNMO) and a narrow biphasic domain (0 < x ≤ 0.3). Remarkably, significant variations are observed in the Raman spectra, which are linked to the activity of the Ni redox system at 4.7 V. It is demonstrated that an appropriate analysis of the bands corresponding to pure Ni–O stretching modes leads to an accurate estimation of the electrode states of charge and depth of discharge, which opens the way for a reliable quantification of the self-discharge phenomenon. The mechanism of Li extraction insertion here pictured for the first time for LNMO thin layers is consistent with their disordered nature and accounts for their good electrochemical performance.

Published
2022

20. Hexaphyrin-cyclodextrin hybrids: Getting larger, getting confused

Author

Bernard Boitrel, François Robert, Stéphane Le Gac, Mickaël Ménand, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), We are grateful to the Agence Nationale de la Recherche for financial support (ANR research program PRALLOCAT, ANR-16-CE07-0014 and MIXAR, ANR-20-CE07-0026)., ANR-16-CE07-0014,PRALLOCAT,Vers des catalyseurs processifs allostériques pour l'encodage moléculaire(2016), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
conformation, chemistry.chemical_classification, Möbius, Cyclodextrin, 010405 organic chemistry, Chemistry, Stereochemistry, Aromaticity, aromaticity, General Chemistry, 010402 general chemistry, 01 natural sciences, hexaphyrin, 0104 chemical sciences, cyclodextrin, Covalent bond, [CHIM]Chemical Sciences, N-confused, Hybrid
Abstract

The diversity of hexaphyrin-cyclodextrin hybrids (HCD), previously formed from the covalent assembly of regular hexaphyrin and [Formula: see text]-cyclodextrin subunits, has been increased following two main directions: enlarging the confined space provided by the cyclodextrin and tuning the N-core of the hexaphyrin aiming at bimetallic complexes. The larger [Formula: see text]-cyclodextrin unit was selectively functionalized with aldehyde linkers on its primary rim which were further reacted with 2 eq. of pentafluorophenyl tripyrrane in acidic conditions, followed by DDQ oxidation. Doubly-linked HCD hybrids were obtained with structural variations in the hexaphyrin macrocycles depending on the MSA concentration (2 vs. 200 mM) producing either regular ([26] rectangular/[28] Möbius) or doubly N-confused dioxo ([26] rectangular) scaffolds. For the latter, two isomers were isolated featuring mirror transoid skeletons and long-side meso-linking patterns, giving rise to planar chirality at the origin of intense and opposite electronic circular dichroism (ECD) spectra. Zn(II) complexation was then investigated leading to two main findings. (i) The regular [28] Möbius HCD afforded a mixture of monometallic Möbius Zn(II) complexes in the presence of acac ligand. ECD spectroscopy indicated a chirality transfer from the [Formula: see text]-cyclodextrin favoring a [Formula: see text] Möbius twist, but opposite to that arising from the narrower [Formula: see text]-cyclodextrin congener ([Formula: see text] twist favored). (ii) Owing to N3O coordination boxes, dissymmetric bimetallic Zn(II) complexes were readily formed with the doubly N-confused dioxo HCDs through a positive cooperative process. Both metal centers bind a DMAP ligand in axial positions, which is of interest for the

Published
2021

21. Chemical Passivation with Phosphonic Acid Derivatives of ZnO Deposited by Atomic Layer Deposition and Its Influence on the Halide Perovskite Interface

Author

Nathanaelle Schneider, Claire Darin Bapaume, Muriel Bouttemy, François Ozanam, Philip Schulz, Olivier Fournier, Laurent Lombez, Davina Messou, Jean Rousset, Institut Photovoltaïque d’Ile-de-France (UMR) (IPVF), École polytechnique (X)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-TOTAL FINA ELF-EDF (EDF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Photovoltaïque d’Ile-de-France (ITE) (IPVF)-Air Liquide [Siège Social], Centre d'études de chimie métallurgique (CECM), Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique de la matière condensée (LPMC), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche et Développement sur l'Energie Photovoltaïque (IRDEP), EDF R&D (EDF R&D), EDF (EDF)-EDF (EDF)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Passivation, Energy Engineering and Power Technology, Infrared spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Atomic layer deposition, X-ray photoelectron spectroscopy, Chemical engineering, Attenuated total reflection, Monolayer, Materials Chemistry, Electrochemistry, Chemical Engineering (miscellaneous), Electrical and Electronic Engineering, 0210 nano-technology, Layer (electronics), Perovskite (structure)
Abstract

International audience; We report on the modification of zinc oxide thin films deposited by atomic layer deposition (ALD-ZnO) with various phosphonic acid derivatives. Particularly, three molecules differing by their spacer and functionalizing groups were tested: 2-aminoethylphosphonic acid (2-AEPA), 4-aminobenzylphosphonic acid (4-ABzPA) and 4-fluorobenzylphosphonic acid (4-FBzPA). The resulting surfaces were investigated with surface sensitive characterization techniques such as X-ray photoelectron spectroscopy and attenuated total reflection IR spectroscopy. We find differences in the phosphonic acid film growth, mostly driven by the nature of the functionalizing group: the amine-based molecules tend to cover the surface with disordered layers or multilayers whereas the 4-FBzPA layer rather exhibits features of a monolayer. Finally, 2-AEPA and 4-FBzPA have been used as a mean to passivate the reactive interface between ALD-ZnO and a hybrid organic inorganic metal halide perovskite. Morphological and structural studies were carried out with scanning electron microscopy and X-ray diffraction and solar cells using these layers as electron transport layers were synthetized. With a highest power conversion efficiency of 4.1%, the direct application of these surface modifications into complete devices is shown not to be enough to achieve high-efficiency solar cells with ALD-ZnO.

Published
2021

22. DNA nuclear targeting sequences for enhanced non-viral gene transfer: An in vitro and in vivo study

Author

Tristan Montier, Philippe Guégan, Sandrine Quemener, Kévin Pluchon, Juliette Ropars, Chantal Pichon, Tanguy Haute, Yann Thierry Le Guen, Tony Le Gall, Patrick Midoux, Gestionnaire, Hal Sorbonne Université, monopDNA-Nanoparticules Virus-Inspirées pour transfert de gènes. - - VINP2017 - ANR-17-CE18-0015 - AAPG2017 - VALID, Génétique, génomique fonctionnelle et biotechnologies (UMR 1078) (GGB), EFS-Université de Brest (UBO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Chimie des polymères (LCP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut Parisien de Chimie Moléculaire (IPCM), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre Hospitalier Régional Universitaire de Brest (CHRU Brest), Récepteurs Nucléaires, Maladies Métaboliques et Cardiovasculaires (RNMCD - U1011), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), This work was funded by grants from the AFM – Association Française contre les Myopathies (project no. AFM2017#20609, AFM, Evry, France), the ANR – Agence Nationale de la Recherche (project no. ANR-17-CE18-0015-03, 'monopDNA-Nanoparticules Virus-Inspirées pour transfert de gènes', ANR, Paris, France), the Association de Transfusion Sanguine et de Biogénétique Gaétan Saleün (Brest, France), and the Région Bretagne (France). The Service Général des Plateformes, Animalerie Commune (Brest, France) and SynNanoVect (Brest-Rennes, France) are also acknowledged. Y.T.L.G. was a recipient of a PhD fellowship from the French Ministry of Higher Education, Research and Innovation., ANR-17-CE18-0015,VINP,monopDNA-Nanoparticules Virus-Inspirées pour transfert de gènes.(2017), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-EFS-Institut National de la Santé et de la Recherche Médicale (INSERM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Récepteurs Nucléaires, Maladies Métaboliques et Cardiovasculaires - U1011 (RNMCD)

Subjects
0301 basic medicine, [SDV]Life Sciences [q-bio], RM1-950, NF-κB, 03 medical and health sciences, chemistry.chemical_compound, 0302 clinical medicine, plasmid DNA, In vivo, Drug Discovery, skeletal muscle, Transcription factor, hydrodynamic limb vein injection, Transfection, nuclear import, In vitro, Cell biology, [SDV] Life Sciences [q-bio], 030104 developmental biology, chemistry, transfection, Cell culture, 030220 oncology & carcinogenesis, Nucleic acid, Molecular Medicine, Therapeutics. Pharmacology, Nuclear transport, DNA
Abstract

International audience; An important bottleneck for non-viral gene transfer commonly relates to translocation of nucleic acids into the nuclear compartment of target cells. So-called 3NFs are optimized short nucleotide sequences able to interact with the transcription factor nuclear factor κB (NF-κB), which can enhance the nuclear import of plasmid DNA (pDNA) carrying such motifs. In this work, we first designed a consistent set of six pDNAs featuring a common backbone and only varying in their 3NF sequences. These constructions were then transfected under various experimental settings. In vitro, cationic polymer-assisted pDNA delivery in five human-derived cell lines showed the potential advantage of 3NF carrying pDNA in diverse cellular contexts. In vivo, naked pDNAs were hydrodynamically delivered to muscle hindlimbs in healthy mice; this direct accurate comparative (in the absence of any gene carrier) revealed modest but consistent trends in favor of the pDNAs equipped with 3NF. In summary, the results reported emphasize the implications of various parameters on NF-κB-mediated pDNA nuclear import; under specific conditions, 3NF can provide modest to substantial advantages for pDNA gene transfer, in vitro as well as in vivo. This study thus further underscores the potential of optimized nuclear import for more efficient non-viral gene transfer applications.

Published
2021

23. NMR studies of adsorption and diffusion in porous carbonaceous materials

Author

Clare P. Grey, Céline Merlet, John M. Griffin, Alexander C. Forse, Department of Chemistry [Cambridge, UK], University of Cambridge [UK] (CAM), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Department of Chemistry [Lancaster], Lancaster University, Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Centre National de la Recherche Scientifique - CNRS (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), University of Cambridge (UNITED KINGDOM), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Réseau de stockage électrochimique de l’énergie - Energie RS2E (FRANCE), Lancaster University (UNITED KINGDOM), Centre Interuniversitaire de Recherche et d'Ingénierie des Matériaux - CIRIMAT (Toulouse, France), and Apollo - University of Cambridge Repository

Subjects
Nuclear and High Energy Physics, Materials science, Matériaux, Diffusion, FOS: Physical sciences, chemistry.chemical_element, Nucleus-independent chemical shift, 010402 general chemistry, 01 natural sciences, Biochemistry, 030218 nuclear medicine & medical imaging, Analytical Chemistry, Ion, 03 medical and health sciences, 0302 clinical medicine, Adsorption, Shielding effect, Molecule, Porosity, Spectroscopy, Condensed Matter - Materials Science, Porous carbons, Materials Science (cond-mat.mtrl-sci), [CHIM.MATE]Chemical Sciences/Material chemistry, Nuclear magnetic resonance spectroscopy, Ring current shielding, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, 13. Climate action, Chemical physics, Carbon
Abstract

Porous carbonaceous materials have many important industrial applications including energy storage, water purification, and adsorption of volatile organic compounds. Most of their applications rely upon the adsorption of molecules or ions within the interior pore volume of the carbon particles. Understanding the behaviour and properties of adsorbate species on the molecular level is therefore key for optimising porous carbon materials, but this is very challenging owing to the complexity of the disordered carbon structure and the presence of multiple phases in the system. In recent years, NMR spectroscopy has emerged as one of the few experimental techniques that can resolve adsorbed species from those outside the pore network. Adsorbed, or "in-pore" species give rise to resonances that appear at lower chemical shifts compared to their free (or "ex-pore") counterparts. This shielding effect arises primarily due to ring currents in the carbon structure in the presence of a magnetic field, such that the observed chemical shift differences upon adsorption are nucleus-independent to a first approximation. Theoretical modelling has played an important role in rationalising and explaining these experimental observations. Together, experiments and simulations have enabled a large amount of information to be gained on the adsorption and diffusion of adsorbed species, as well as on the structural and magnetic properties of the porous carbon adsorbent. Here, we review the methodological developments and applications of NMR spectroscopy and related modelling in this field, and provide perspectives on possible future applications and research directions.

Published
2021

24. Towards a better understanding of the degradation mechanisms of Li-ion full cells using Si/C composites as anode

Author

Mariana Gutierrez, Mathieu Morcrette, Laure Monconduit, Yohan Oudart, Pierre Lemaire, Carine Davoisne, Nicolas Louvain, Raphaël Janot, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Nanomakers, Recherche Opérationnelle pour les Systèmes de Production (G-SCOP_ROSP), Laboratoire des sciences pour la conception, l'optimisation et la production (G-SCOP), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Renewable Energy, Sustainability and the Environment, Energy Engineering and Power Technology, [CHIM]Chemical Sciences, [CHIM.MATE]Chemical Sciences/Material chemistry, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; Carbon-coated silicon nanoparticles (40 nm diameter) were used to prepare pitch-based Si/C composites with different Si contents and a pitch and graphite-based Si/C/Gr composite. These composites were prepared by pyrolysis at 900 °C of a pitch/Si mixture obtained from the dispersion of Si particles in a solution of pitch in THF. The as-prepared composites delivered high coulombic efficiencies at the first cycle (83–86%) and stable reversible capacities (560–650 mAh g−1) versus lithium. The anodes degradation phenomena while cycling versus NMC622 in a full cell configuration were studied by simple electrochemical tests such as analysing the harvested electrodes in half-cells vs. lithium. The clear improvement on electrochemical performances due to the graphite addition was demonstrated with the suppression of the active particle's disconnection. The pitch and graphite-based composite was proven to accommodate well the silicon volume expansion and to deliver a stable electrochemical capacity of 650 mAh g−1 at the rate of C/5.

Published
2022

25. Mathematical Modeling of Energy-dense NMC Electrodes: Part II. Data Analysis with Newman Model and with an Extended Model Accounting for Particle Agglomeration

Author

Tuan-Tu Nguyen, Bruno Delobel, Arnaud Demortière, Charles Delacourt, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Technocentre Renault [Guyancourt], RENAULT, Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
[CHIM.GENI]Chemical Sciences/Chemical engineering, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Renewable Energy, Sustainability and the Environment, Materials Chemistry, Electrochemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Condensed Matter Physics, [SPI.MAT]Engineering Sciences [physics]/Materials, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract

International audience; In this second part of this series of papers, the use of two physics-based models to analyze the discharge performance of a set of high-energy-density electrodes is discussed. The measured set of parameters from the first part is implemented into these models. First, the regular Newman pseudo-2D model shows a large discrepancy against the experimental values. Then, an extension of the Newman model considering the particle agglomeration due to the calendering effects is presented, allowing for the validation of discharge rate capabilities of all studied industry-grade electrodes with different electrolytes. At the agglomerate scale, the model accounts for both the ionic transport in sub-pores and the inter-particle solid diffusion. The simulation results from this work demonstrate that increasing the electrode loading and/or density leads to either a higher fraction of sub-pores (at the expense of that of macropores) or larger porous agglomerate size, resulting in a poor rate performance. The model analysis suggests that a substantial gain in performance at high C-rates is expected if agglomeration effects are mitigated in these high-energy electrodes.

Published
2022

26. Phenyl Silicates with Substituted Catecholate Ligands: Synthesis, Structural Studies and Reactivity

Author

Heng-Rui Zhang, Etienne Derat, Louis Fensterbank, Aurélie Bernard, Etienne Levernier, Khaoula Jaouadi, Geoffrey Gontard, Laurence Grimaud, Cyril Ollivier, Vincent Corcé, Claire Troufflard, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Méthodes et Application en Chimie Organique (MACO), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Ollivier, Cyril

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Ligand, Aryl, Radical, Organic Chemistry, Photoredox catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Moiety, Reactivity (chemistry), Alkyl
Abstract

International audience; While the generation of aryl radicals by photoredox catalysis is well-documented under reductive conditions, it has remained challenging under an oxidative pathway. Because of the easy photooxidation of alkyl bis-catecholato silicates, a general study on phenyl silicates bearing substituted catecholate ligands has been achieved. The newly synthesized phenyl silicates have been fully characterized and their reactivity has been explored. It was found that thanks to the substitution of the catecholate moiety and notably with the 4-cyanocatecholato ligand, the phenyl radical could be generated and trapped. Computational studies provided a rationale for these findings.

Published
2021

27. Photochromism and Persistent Luminescence in Ni-Doped ZnGa2O4 Transparent Glass-Ceramics: Toward Optical Memory Applications

Author

Didier Gourier, Luidgi Giordano, Bruno Viana, Mathieu Allix, Cyrille Richard, Victor Castaing, Institut de Recherche de Chimie Paris (IRCP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Unité de Technologies Chimiques et Biologiques pour la Santé (UTCBS - UM 4 (UMR 8258 / U1022)), Institut de Chimie du CNRS (INC)-Université de Paris (UP)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ORANGE, Colette

Subjects
MECHANISM, LONG-PERSISTENT, Materials science, Infrared, EUROPIUM, chemistry.chemical_element, Phosphor, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Photochromism, Persistent luminescence, NANOPARTICLES, Ceramic, Physical and Theoretical Chemistry, TRAP DEPTH, [CHIM.MATE] Chemical Sciences/Material chemistry, SPECTROSCOPY, business.industry, Doping, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, General Energy, chemistry, visual_art, visual_art.visual_art_medium, 2-PHOTON EXCITATION, Optoelectronics, VISIBLE-LIGHT, 0210 nano-technology, business, Europium, PEROVSKITE PHOSPHOR, STORAGE, Visible spectrum
Abstract

International audience; Persistent luminescence and photochromism are two fascinating optical properties that involve charge trapping via defects and their release due to an external stimulation. In both processes, it is possible to define 1 (or on) and 0 (or off) optical states. Consequently, materials with one of these phenomena find major interest in view of designing smart, anticounterfeiting, and optical information storage devices. Combining both processes within a single material can lead to a new generation of information storage phosphors, in which it may be possible to obtain three different optical states by playing on the external stimulations applied on the material. For that purpose, the elaboration of nickel-doped ZnGa2O4 spinet transparent nano-glassceramics is presented in this work. The short-wave infrared (SWIR) emission, a broad band located at ca. 1275 nm, arises from Ni2+ cations located in gallium octahedral sites. SWIR persistent luminescence, arising from the same doping ion transition, can also be monitored after UV charging. Interestingly, UV irradiation not only leads to persistent luminescence charging but also to a reversible photochromism effect. By means of a complete optical characterization study combined with electron paramagnetic resonance measurements, the origins of both the persistent luminescence emission and the photochromism are explored. Finally, a discussion on the advantages of such a material combining both persistent luminescence and photochromism properties, leading to three possible optical states of the material, is dressed in view of possible optical memory systems.

Published
2021

28. Dissection of the anti-Candida albicans mannan immune response using synthetic oligomannosides reveals unique properties of β-1,2 mannotriose protective epitopes

Author

Sébastien Damiens, Faustine Dubar, Samir Jawhara, Boualem Sendid, Mayeul Collot, Karine Lecointe, Jean-Maurice Mallet, Anne-Sophie Drucbert, Daniel Poulain, Chantal Fradin, Pierre-Marie Danzé, Jean-Pierre Vilcot, Jérôme de Ruyck, Frédéric Grenouillet, Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), Facteurs de Risque et Déterminants Moléculaires des Maladies liées au Vieillissement - U 1167 (RID-AGE), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Optoélectronique - IEMN (OPTO - IEMN), INSA Institut National des Sciences Appliquées Hauts-de-France (INSA Hauts-De-France), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Centre Hospitalier Régional Universitaire de Besançon (CHRU Besançon), We thank the European Union for funding through the INTERREG V France—Wallonie—Vlaanderen program—SmartBioControl-BIOSENS project and the Programme Hospitalier de Recherche Clinique, CandiGene, 2011–1918., Unité de Glycobiologie Structurale et Fonctionnelle (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Laboratoire des biomolécules [LBM UMR 7203], Institut de Pathologie [CHU Lille], Laboratoire de Bioimagerie et Pathologies [LBP], Médicaments et biomatériaux à libération contrôlée: mécanismes et optimisation - Advanced Drug Delivery Systems - U 1008 [MBLC - ADDS], Lille Inflammation Research International Center - U 995 [LIRIC], Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 [IEMN], Laboratoire Chrono-environnement (UMR 6249) [LCE], Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 [UGSF], and Collot, Mayeul

Subjects
Antigens, Fungal, medicine.drug_class, [SDV]Life Sciences [q-bio], Science, Immunology, Oligosaccharides, Monoclonal antibody, Biochemistry, Microbiology, Article, Epitope, Mannans, 03 medical and health sciences, Antigen, Antibody Specificity, Candida albicans, medicine, 030304 developmental biology, Mannan, 0303 health sciences, Multidisciplinary, biology, 030306 microbiology, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Candidiasis, Antibodies, Monoclonal, Surface Plasmon Resonance, [CHIM.ORGA] Chemical Sciences/Organic chemistry, biology.organism_classification, Chemical biology, Corpus albicans, 3. Good health, [SDV] Life Sciences [q-bio], Polyclonal antibodies, biology.protein, Medicine, Antibody, Trisaccharides, Epitope Mapping
Abstract

Candida albicans mannan consists of a large repertoire of oligomannosides with different types of mannose linkages and chain lengths, which act as individual epitopes with more or less overlapping antibody specificities. Although anti-C. albicans mannan antibody levels are monitored for diagnostic purposes nothing is known about the qualitative distribution of these antibodies in terms of epitope specificity. We addressed this question using a bank of previously synthesized biotin sulfone tagged oligomannosides (BSTOs) of α and β anomery complemented with a synthetic β-mannotriose described as a protective epitope. The reactivity of these BSTOs was analyzed with IgM isotype monoclonal antibodies (MAbs) of known specificity, polyclonal sera from patients colonized or infected with C. albicans, and mannose binding lectin (MBL). Surface plasmon resonance (SPR) and multiple analyte profiling (MAP) were used. Both methods confirmed the usual reactivity of MAbs against either α or β linkages, excepted for MAb B6.1 (protective epitope) reacting with β-Man whereas the corresponding BSTO reacted with anti-α-Man. These results were confirmed in western blots with native C. albicans antigens. Using patients’ sera in MAP, a significant correlation was observed between the detection of anti-mannan antibodies recognizing β- and α-Man epitopes and detection of antibodies against β-linked mannotriose suggesting that this epitope also reacts with human polyclonal antibodies of both specificities. By contrast, the reactivity of human sera with other α- and β-linked BSTOs clearly differed according to their colonized or infected status. In these cases, the establishment of an α/β ratio was extremely discriminant. Finally SPR with MBL, an important lectin of innate immunity to C. albicans, classically known to interact with α-mannose, also interacted in an unexpected way with the protective epitope. These cumulative data suggest that structure/activity investigations of the finely tuned C. albicans anti-mannose immune response are worthwhile to increase our basic knowledge and for translation in medicine.

Published
2021

29. Asymmetric micro-supercapacitors based on electrodeposited Ruo2 and sputtered VN films

Author

Christophe Lethien, Thierry Brousse, Kevin Robert, Bouchra Asbani, Pascal Roussel, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Circuits Systèmes Applications des Micro-ondes - IEMN (CSAM - IEMN ), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This research benefitted from the financial support of the ANR within the DENSSCAPIO project (ANR-17-CE05–0015–02). The authors would also like to thank the ANR STORE-EX and the RS2E for their financial support. The RENATECH network receives our utmost gratitude. Chevreul Institute (CNRS FR 2638), Ministère de l’Enseignement Supérieur et de la Recherche, Région Hauts de France and FEDER are acknowledged for supporting and funding XRD facilities., RS2E, Renatech Network, CMNF, ANR-17-CE05-0015,DENSSCAPIO,Supercondensateurs nanostructurés tout-solides pour stockage d'énergie plus dense et plus sûr(2017), ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), CNRS, Centrale Lille, ENSCL, ISEN, Institut Catholique Lille, Univ. Artois, Univ. Valenciennes, Université de Lille, Institut d'Électronique, de Microélectronique et de Nanotechnologie (IEMN) - UMR 8520, and Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181

Subjects
Materials science, Vanadium nitride, Energy Engineering and Power Technology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Capacitance, Ruthenium oxide, vanadium nitride, chemistry.chemical_compound, asymmetric micro-supercapacitors, Sputtering, General Materials Science, Thin film, Electrochemical potential, Power density, Supercapacitor, Renewable Energy, Sustainability and the Environment, business.industry, [SPI.NRJ]Engineering Sciences [physics]/Electric power, hydrous ruthenium oxide, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, thin films, chemistry, electrodeposition, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Optoelectronics, sputtering, 0210 nano-technology, business
Abstract

International audience; Research on micro-supercapacitors remains one of the most important activities in the area of electrochemical energy storage for powering smart and miniaturized electronic devices. Here we design an asymmetric micro-supercapacitor (A-MSC) combining sputtered vanadium nitride film (VN) and electrodeposited hydrous ruthenium oxide (hRuO2) film. Taking advantage of their complementary electrochemical potential windows in 1 M KOH electrolyte, the A-MSC achieves a cell voltage up to 1.15 V, associated to high specific capacitance values for the device (≈ 100 mF cm−2). The energy density of this asymmetric VN / hRuO2 micro-supercapacitor reaches 20 µWh cm−2 at a power density of 3 mW cm−2. Taking benefit from the asymmetric configuration, a 5-fold enhancement factor in energy density is demonstrated for the VN / hRuO2 asymmetric micro-supercapacitor as compared to symmetric VN / VN and hRuO2 / hRuO2 microdevices.

Published
2021

30. How wide is the window opened by high-resolution relaxometry on the internal dynamics of proteins in solution?

Author

Nicolas Bolik-Coulon, Matthias Ernst, Fabien Ferrage, Albert A. Smith, Beat H. Meier, Universität Leipzig [Leipzig], Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), and Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich)

Subjects
Relaxometry, 010402 general chemistry, 01 natural sciences, Biochemistry, Article, [CHIM]Chemical Sciences, Isoleucine, Nuclear Magnetic Resonance, Biomolecular, Spectroscopy, Detector analysis, Ubiquitin, 010405 organic chemistry, Chemistry, Protein dynamics, Resolution (electron density), Relaxation (NMR), Dynamics (mechanics), Detector, Proteins, Rotational diffusion, Nanosecond, Dynamics, 0104 chemical sciences, Solutions, Chemical physics, Solution-state NMR
Abstract

The dynamics of molecules in solution is usually quantified by the determination of timescale-specific amplitudes of motions. High-resolution nuclear magnetic resonance (NMR) relaxometry experiments—where the sample is transferred to low fields for longitudinal (T1) relaxation, and back to high field for detection with residue-specific resolution—seeks to increase the ability to distinguish the contributions from motion on timescales slower than a few nanoseconds. However, tumbling of a molecule in solution masks some of these motions. Therefore, we investigate to what extent relaxometry improves timescale resolution, using the “detector” analysis of dynamics. Here, we demonstrate improvements in the characterization of internal dynamics of methyl-bearing side chains by carbon-13 relaxometry in the small protein ubiquitin. We show that relaxometry data leads to better information about nanosecond motions as compared to high-field relaxation data only. Our calculations show that gains from relaxometry are greater with increasing correlation time of rotational diffusion., Journal of Biomolecular NMR, 75 (2-3), ISSN:0925-2738, ISSN:1573-5001

Published
2021

31. Confining Water in Ionic and Organic Solvents to Tune Its Adsorption and Reactivity at Electrified Interfaces

Author

Alexis Grimaud, Mathieu Salanne, Nicolas Dubouis, Alessandra Serva, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), and ANR-19-CE05-0014,BALWISE,Batteries aqueuses au Li utilisant des électrolytes superconcentrés(2019)

Subjects
[PHYS]Physics [physics], Aqueous solution, 010405 organic chemistry, Chemistry, Ionic bonding, General Medicine, General Chemistry, Electrolyte, 010402 general chemistry, 01 natural sciences, Article, 0104 chemical sciences, Adsorption, Chemical engineering, Reactivity (chemistry)
Abstract

International audience; ConspectusThe recent discovery of "water-in-salt" electrolytes has spurred a rebirth of research on aqueous batteries. Most of the attention has been focused on the formulation of salts enabling the electrochemical window to be expanded as much as possible, well beyond the 1.23 V allowed by thermodynamics in water. This approach has led to critical successes, with devices operating at voltages of up to 4 V. These efforts were accompanied by fundamental studies aiming at understanding water speciation and its link with the bulk and interfacial properties of water-in-salt electrolytes. This speciation was found to differ markedly from that in conventional aqueous solutions since most water molecules are involved in the solvation of the cationic species (in general Li+) and thus cannot form their usual hydrogen-bonding network. Instead, it is the anions that tend to self-aggregate in nanodomains and dictate the interfacial and transport properties of the electrolyte. This particular speciation drastically alters the presence and reactivity of the water molecules at electrified interfaces, which enlarges the electrochemical windows of these aqueous electrolytes.Thanks to this fundamental understanding, a second very active lead was recently followed, which consists of using a scarce amount of water in nonaqueous electrolytes in order to control the interfacial properties. Following this path, it was proposed to use an organic solvent such as acetonitrile as a confinement matrix for water. Tuning the salt/water ratio in such systems leads to a whole family of systems that can be used to determine the reactivity of water and control the potential at which the hydrogen evolution reaction occurs. Put together, all of these efforts allow a shift of our view of the water molecule from a passive solvent to a reactant involved in many distinct fields ranging from electrochemical energy storage to (electro)catalysis.Combining spectroscopic and electrochemical techniques with molecular dynamics simulations, we have observed very interesting chemical phenomena such as immiscibility between two aqueous phases, specific adsorption properties of water molecules that strongly affect their reactivity, and complex diffusive mechanisms due to the formation of anionic and aqueous nanodomains.

Published
2021

32. Different ion mobility‐mass spectrometry coupling techniques to promote metabolomics

Author

Sandra Alves, Estelle Rathahao-Paris, Aurélie Delvaux, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), ANR-11-INBS-0010,METABOHUB,Développement d'une infrastructure française distribuée pour la métabolomique dédiée à l'innovation(2011), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
0301 basic medicine, Ion-mobility spectrometry, Mass spectrometry, 01 natural sciences, Mass Spectrometry, General Biochemistry, Genetics and Molecular Biology, Workflow, Analytical Chemistry, 03 medical and health sciences, Human health, Metabolomics, Ion Mobility Spectrometry, Metabolome, Humans, Spectroscopy, [PHYS]Physics [physics], Chemistry, 010401 analytical chemistry, hyphenated method, Condensed Matter Physics, metabolomics, 0104 chemical sciences, 030104 developmental biology, Untargeted metabolomics, Clinical diagnosis, Chemical diversity, Ion mobilitymass spectrometry, Biochemical engineering, multidimensional data
Abstract

International audience; Metabolomics has become increasingly popular in recent years for many applications ranging from clinical diagnosis, human health to biotechnological questioning. Despite technological advances, metabolomic studies are still currently limited by the difficulty of identifying all metabolites, a class of compounds with great chemical diversity. Although lengthy chromatographic analyses are often used to obtain comprehensive data, many isobar and isomer metabolites still remain unresolved, which is a critical point for the compound identification. Currently, ion mobility spectrometry is being explored in metabolomics as a way to improve metabolome coverage, analysis throughput and isomer separation. In this review, all the steps of a typical workflow for untargeted metabolomics are discussed considering the use of an ion mobility instrument. An overview of metabolomics is first presented followed by a brief description of ion mobility instrumentation. The ion mobility potential for complex mixture analysis is discussed regarding its coupling with a mass spectrometer alone, providing gas-phase separation before mass analysis as well as its combination with different separation platforms (conventional hyphenation but also multidimensional ion mobility couplings), offering multidimensional separation. Various instrumental and analytical conditions for improving the ion mobility separation are also described. Finally, data mining, including software packages and visualization approaches, as well as the construction of ion mobility databases for the metabolite identification are examined.

Published
2021

33. Intercalation–exfoliation processes during ionic exchange reactions from sodium lepidocrocite-type titanate toward a proton-based trititanate structure

Author

Seongkoo Kang, Olivier Dubrunfaut, Serge Durand-Vidal, Monique Body, Christophe Legein, Damien Dambournet, Jean-Claude Badot, Olaf J. Borkiewicz, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut de Recherche de Chimie Paris (IRCP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Argonne National Laboratory [Lemont] (ANL), Laboratoire Génie électrique et électronique de Paris (GeePs), CentraleSupélec-Sorbonne Université (SU)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC)

Subjects
Hydronium, Chemistry, Intercalation (chemistry), Inorganic chemistry, Oxide, General Physics and Astronomy, Ionic bonding, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Exfoliation joint, Titanate, 0104 chemical sciences, Ion, Metal, chemistry.chemical_compound, visual_art, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract

International audience; Topochemical reactions involving ionic exchange have been used to assess a large number of metastable compositions, particularly in layered metal oxides. This method encompasses complex reactions that are poorly explored, yet are of prime importance to understand and control the materials' properties. In this work, we embark on investigating the reactions involved during the ionic exchange between a layered Na-titanate (lepidocrocite-type structure) and an acidic solution (HCl), leading to a protonic (H3O+) titanate (trititanate structure). The reactions involve an ionic exchange provoking a structural change from the lepidocrocite-type to the trititanate structure as shown by real-space refinements of ex situ pair distribution function data. Mobile Na+ ions are exchanged by hydronium ions inducing high proton mobility in the final structure. Moreover, the reaction was followed by ex situ 23Na and 1H solid-state MAS NMR which allowed, among other things, confirming that the Na+ ions are in the interlayer space and specifying their local environment. Strikingly, the ionic exchange reaction induces progressive exfoliation of the Na-titanate particles leading to 2-5 nm thin elongated crystallites. To further understand the different steps associated with the ionic exchange, the evolution of the electrolytic conductivity, using conductimetric titration, has been monitored upon HCl addition, enabling characterization of the intercalation(H+)/de-intercalation(Na+) reactions and assessing kinetic parameters. Accordingly, it is hypothesized that the exfoliation of the particles is due to the accumulation of charges at the particle level in relation to the rapid intercalation of protons. This work provides novel insights into ionic exchange reactions involved in layered oxide compounds.

Published
2021

34. Revisiting the five-decade-old structure of the Fe2WO6 powder with incommensurate modulations

Author

Julio César Espinosa-Angeles, Thierry Brousse, Olivier Joubert, Olivier Crosnier, Eric Quarez, Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Diffraction, Materials science, Condensed matter physics, 02 engineering and technology, General Chemistry, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Superspace, Electrochemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Tungstate, chemistry, Modulation (music), Thermoelectric effect, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], General Materials Science, 0210 nano-technology, Powder diffraction
Abstract

International audience; Iron tungstate, Fe2WO6, is a promising photocatalytic, thermoelectric and electrochemically active material for energy storage devices. However, its structure is poorly described in the literature reporting on these applications. For the first time, we solved the crystal structure of its high temperature form using powder X-ray diffraction and the incommensurately modulated structural model. The structure adopts a (3 + 1)-dimensional Pbcn(0 beta 0)000 superspace group with the cell parameters a = 4.57964(7) angstrom, b = 5.58662(8) angstrom, and c = 4.96920(7) angstrom and the modulation vector q = 0.6687(4) b*, close to the commensurate case q = 2/3 b*. The first-order satellite reflections visible in the powder diffraction patterns show, compared to the main reflections, a substantial broadening of the diffraction lines, caused by the small size of the ordered domains. This broadening has been successfully described using a line-broadening model, designed for incommensurately modulated structures, and confirms the incommensurate structural description. Such findings can be of great help to further understand the reported physical and electrochemical properties.

Published
2021

35. Effect of the electron donating group on the excited-state electronic nature and epsilon-near-zero properties of curcuminoid-borondifluoride dyes

Author

Dandan Yao, Loic Mager, Elena Zaborova, Kyu-Ri Choi, Benoît Heinrich, Gabriel Canard, Frédéric Fages, Jean Charles Ribierre, Anthony D'Aléo, Steven Huynh, Dae Hyeon Kim, Yeon Ui Lee, Fabrice Mathevet, Jeong Weon Wu, Virginie Placide, EWHA Womans University (EWHA), Chungbuk National University, Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Kyushu University [Fukuoka], D'Aléo, Anthony, Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Kyushu University

Subjects
Epsilon-near-zero, Materials science, Curcuminoid, General Chemical Engineering, Physics::Optics, 02 engineering and technology, Electron, 01 natural sciences, 010309 optics, Physics::Popular Physics, Condensed Matter::Materials Science, Organic thin film, chemistry.chemical_compound, Condensed Matter::Superconductivity, [CHIM] Chemical Sciences, 0103 physical sciences, Molecular film, [CHIM]Chemical Sciences, Cyanine, Thin film, General Chemistry, 021001 nanoscience & nanotechnology, Acceptor, Computer Science::Computers and Society, Crystallography, Character (mathematics), chemistry, Excited state, 0210 nano-technology, Visible spectrum
Abstract

Epsilon-near-zero (ENZ) properties have been reported in organic molecular films. In particular, cyanine and squaraine films have been shown to exhibit ENZ properties in the visible spectral region with a strong 3rd order nonlinear optical response near the ENZ spectral region. Noting both cyanine and squaraine belong to the polymethine family, a series of six curcuminoid borondifluoride (Curc) derivatives were developed to examine whether such a polymethine character is positively correlated with the ENZ property of the organic films. Those Curc derivatives possess a Donor–Acceptor–Donor (D–A–D) architecture with acceptor, AcacBF2, located at the molecular center. The backbone of Curc is designed such that the donor strength can be tuned to transit between charge transfer (CT) and polymethine character. This balance between CT and polymethine character of the Curc series is examined based on the Lippert–Mataga plot. As donor strength in the D–A–D structure increases, CT character is less marked resulting in a more dominant polymethine character. The structural and optical properties of the Curc films with a thickness in the order of 30 nm were examined to correlate the polymethine character with the ENZ response. The results obtained in isotropic Curc thin films demonstrate that an increase of polymethine character associated with a stronger donor strength leads to an appearance/enhancement of the ENZ property in the visible spectrum range from 500 to 670 nm. Overall, this study provides useful guidelines to engineer new organic materials showing ENZ properties in a desired spectral range.

Published
2021

36. Hard carbon key properties allow for the achievement of high Coulombic efficiency and high volumetric capacity in Na-ion batteries

Author

François Rabuel, Mathieu Morcrette, Camelia Matei Ghimbeu, Stephan Knopf, Patrice Simon, Pierre-Louis Taberna, Adrian Beda, Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université de Toulouse (UT)

Subjects
Materials science, Renewable Energy, Sustainability and the Environment, chemistry.chemical_element, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 7. Clean energy, 01 natural sciences, 0104 chemical sciences, Chemical engineering, chemistry, Specific surface area, Electrode, [CHIM]Chemical Sciences, Particle, General Materials Science, Graphite, 0210 nano-technology, Porosity, Carbon, Faraday efficiency
Abstract

International audience; The volumetric capacity and the initial Coulombic efficiency are features of major importance when it comes to the development of full-cell batteries, and are thus key characteristics to boost Na-ion batteries (NIBs) commercialization. To allow the improvement of these parameters, several hard carbon properties that are rarely addressed, such as tapped density and electrode porosity after calendaring, were investigated herein in relation with their physico-chemical characteristics and electrochemical performance. A series of sustainable and scalable synthesized hard carbon spheres with controlled properties were used in this purpose. It was found that the electrode porosity after calendaring decreases rather linearly with the graphite interlayer space (d002), the lowest value (41%) being reached for high temperature treated carbons (>1500 °C). No clear correlation could be established between the electrode porosity and the tapped density. This could be understood by the dependence of the tapped density on several interplaying parameters, including the porosity (open, closed and inter-grain) and the morphology (particle shape and size). The compact carbon electrodes could deliver a high volumetric capacity of ∼300 mA h cm−3. Such performance was achieved by combining low electrode porosity, low interlayer space, and low specific surface area as emphasized by comparison with several other lab-made and commercial hard carbons. Moreover, these carbon spheres revealed an initial Coulombic efficiency of 92%, which is among the highest value reported for hard carbon. This could be correlated in large extent with the low values of the specific surface area of ultra-micropores (

Published
2021

37. Tunable UCST thermoresponsive copolymers based on natural glycyrrhetinic acid

Author

Yiran Zhao, Xia Yu, Min-Hui Li, Jingyao Ma, Jun Hu, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche de Chimie Paris (IRCP), Ministère de la Culture (MC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Beijing University of Chemical Technology, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC)

Subjects
UCST, natural product, Materials science, glycyrrhetinic acid, thermo-responsive polymer, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Lower critical solution temperature, Miscibility, Upper critical solution temperature, Copolymer, [CHIM]Chemical Sciences, Thermoresponsive polymers in chromatography, ComputingMilieux_MISCELLANEOUS, [PHYS]Physics [physics], chemistry.chemical_classification, Chain transfer, General Chemistry, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, cyclodextrin, Polymerization, chemistry, Chemical engineering, 0210 nano-technology
Abstract

International audience; Water-soluble thermoresponsive polymers present either upper critical solution temperature (UCST) or lower critical solution temperature (LCST) depending on the location of their miscibility range with water at high temperatures or at low temperatures. Compared with LCST polymers, the water-soluble UCST polymers are still less explored until now. In this work three copolymers of P(AAm-co-GAA) were synthesized by copolymerizing two acrylamide monomers, acrylamide (AAm) and acrylamide functionalized with natural glycyrrhetinic acid (GAA), using reversible addition-fragmentation chain transfer (RAFT) polymerization. These copolymers exhibited the typical UCST thermoresponsive behavior, and their phase transition temperatures could be easily tuned to around 37 C for potential biological applications. Moreover, the UCST of P(AAm-co-GAA) can be adjusted not only by the content of glycyrrhetinic acid (GA) and polymer concentrations, but also by the host-guest interactions between GA and cyclodextrins (β-and g-CD). The suitable value of UCST and the biocompatible nature of GA and CDs may endow these copolymers with practical applications in biomedical chemistry

Published
2021

38. How reproducible are surface areas calculated from the BET equation?

Author

Christian Serre, Peyman Z. Moghadam, Feng P, Rama Oktavian, Lin R, Ting, Telalovic S, Omar M. Yaghi, Mark D. Allendorf, Russell E. Morris, Muhammad Sadiq, Philip L. Llewellyn, Jonathan L. Snider, Stavila, Matthew J. Rosseinsky, Hou B, Pütz A, Daniel W. Siderius, Rowlandson J, Randall Q. Snurr, van der Veen M, Nguyen T, Kaneko K, Linares N, Félix Zamora, Zhou H, Camille Petit, Sebastian T. Emmerling, Aran Lamaire, Cui Y, David G. Madden, Salcedo-Abraira P, Krista S. Walton, Soumya Mukherjee, Karam B. Idrees, Doheny Pw, Timur Islamoglu, Azevedo Dcs, Conchi O. Ania, Bu X, Zang X, Martin Schröder, Vilarrasa-García E, Michael T. Huxley, Ken-ichi Otake, Sanchez E, Rega D, Vanspeybroeck, Georges Mouchaham, Carmen Montoro, Lee Sj, David Danaci, Goncalves Rb, Yamil J. Colón, Patricia Horcajada, David S. Sholl, David Fairen-Jimenez, Shane G. Telfer, Bethany M. Connolly, Christian J. Doonan, Ryan P. Lively, D’Alessandro D, Raffaele Ricco, Paul S. Wheatley, Clowes R, Bettina V. Lotsch, Alexandros P. Katsoulidis, François-Xavier Coudert, Dominic Bara, Garcia-Martinez J, Carlos Martí-Gastaldo, Yavuz C, Chen B, Matthew R. Hill, Ross S. Forgan, Shuhei Furukawa, Ghosha Sk, Johannes W.M. Osterrieth, Jack D. Evans, Jorge A. R. Navarro, Suarez Ja, Zhang B, João Marreiros, Jorge Gascon, Neil R. Champness, Kenvin J, Yang S, Iiyuka T, Nakul Rampal, Daniel Maspoch, falcaro p, Rampersad J, Han X, Jacopo Andreo, Benoit Coasne, Yang H, Angelo K, Stefan Wuttke, Santos Bf, Chenyue Sun, Susumu Kitagawa, Luka Skoric, Moreton Jc, Rob Ameloot, Muñoz N, DeWitt Sja, Uemura T, Sven Rogge, Seda Keskin, Lukas W. Bingel, Raghuram Thyagarajan, Mircea Dincă, Seth M. Cohen, Bunzen H, Kukobat R, Omar K. Farha, Sarah L. Griffin, Chen L, University of St Andrews. EaSTCHEM, University of St Andrews. School of Chemistry, University of St Andrews. Institute of Behavioural and Neural Sciences, Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), University of Cambridge [UK] (CAM), Sandia National Laboratories [Livermore], Sandia National Laboratories - Corporation, Catholic University of Leuven - Katholieke Universiteit Leuven (KU Leuven), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidade Federal do Ceará = Federal University of Ceará (UFC), Nankai University (NKU), University of Augsburg (UNIA), University of Nottingham, UK (UON), The University of Texas at San Antonio (UTSA), Laboratoire Interdisciplinaire de Physique [Saint Martin d’Hères] (LIPhy ), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), University of California [San Diego] (UC San Diego), University of California (UC), University of Notre Dame [Indiana] (UND), University of Liverpool, Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Shanghai Jiaotong University, The University of Sydney, Massachusetts Institute of Technology (MIT), University of Adelaide, Technische Universität Dresden = Dresden University of Technology (TU Dresden), Graz University of Technology [Graz] (TU Graz), Northwestern University [Evanston], University of California [Riverside] (UC Riverside), University of Glasgow, Kyoto University, King Abdullah University of Science and Technology (KAUST), Indian Institute of Science Education and Research Pune (IISER Pune), Monash university, Instituto IMDEA Energy [Madrid], Instituto IMDEA Energía, Shinshu University [Nagano], Koç University, Georgia Institute of Technology [Atlanta], TotalEnergies, Aix Marseille Université (AMU), Centre National de la Recherche Scientifique (CNRS), Max Planck Institute for Solid State Research, Max-Planck-Gesellschaft, Ludwig-Maximilians-Universität München (LMU), Universitat de València (UV), Universidad de Alicante, Barcelona Institute of Science and Technology (BIST), University of Sheffield [Sheffield], University of Saint Andrews, Universidad de Granada = University of Granada (UGR), Imperial College London, University of Manchester [Manchester], École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Institute of Standards and Technology [Gaithersburg] (NIST), Massey University, University of Bristol [Bristol], The University of Tokyo (UTokyo), Delft University of Technology (TU Delft), Universiteit Gent = Ghent University (UGENT), Ikerbasque - Basque Foundation for Science, University of California [Berkeley] (UC Berkeley), Korea Advanced Institute of Science and Technology (KAIST), Universidad Autónoma de Madrid (UAM), Texas A&M University [College Station], Universidad de Alicante. Departamento de Química Inorgánica, Laboratorio de Nanotecnología Molecular (NANOMOL), European Commission, European Research Council, University of Cambridge, Trinity College Cambridge, National Nuclear Security Administration (US), Department of Energy (US), Alexander von Humboldt Foundation, Center for Advancing Electronics Dresden, Science and Engineering Research Board (India), Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Research Foundation - Flanders, Engineering and Physical Sciences Research Council (UK), National Research Foundation of Korea, Indonesia Endowment Fund for Education, National Institute of Standards and Technology (US), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Avcı, Seda Keskin (ORCID 0000-0001-5968-0336 & YÖK ID 40548), Osterrieth, J.W.M., Rampersad, J., Madden, D., Rampal, N., Skoric, L., Connolly, B., Allendorf, M.D., Stavila, V., Snider, J.L., Ameloot, R., Marreiros, J., Ania, C., Azevedo, D., Vilarrasa-Garcia, E., Santos, B.F., Bu, X.H., Chang, Z., Bunzen, H., Champness, N.R., Griffin, S.L., Chen, B., Lin, R.B., Coasne, B., Cohen, S., Moreton, J.C., Colón, Y.J., Chen, L., Clowes, R., Coudert, F.X., Cui, Y., Hou, B., D'Alessandro, D.M., Doheny, P.W., Dinc?, M., Sun, C., Doonan, C., Huxley, M.T., Evans, J.D., Falcaro, P., Ricco, R., Farha, O., Idrees, K.B., Islamoglu, T., Feng, P., Yang, H., Forgan, R.S., Bara, D., Furukawa, S., Sanchez, E., Gascon, J., Telalovi?, S., Ghosh, S.K., Mukherjee, S., Hill, M.R., Sadiq, M.M., Horcajada, P., Salcedo-Abraira, P., Kaneko, K., Kukobat, R., Kenvin, J., Kitagawa, S., Otake, K.I., Lively, R.P., DeWitt, S.J.A., Llewellyn, P., Lotsch, B.V., Emmerling, S.T., Pütz, A.M., Martí-Gastaldo, C., Padial, N.M., García-Martínez, J., Linares, N., Maspoch, D., Suárez Del Pino, J.A., Moghadam, P., Oktavian, R., Morris, R.E., Wheatley, P.S., Navarro, J., Petit, C., Danacı, D., Rosseinsky, M.J., Katsoulidis, A.P., Schröder, M., Han, X., Yan, S., Serre, C., Mouchaham, G., Sholl, D.S., Thyagarajan, R., Siderius, D., Snurr, R.Q., Goncalves, R.B., Telfer, S., Lee, S.J., Ting, V.P., Rowlandson, J.L., Uemura T, Iiyuka, T., van derVeen, Monique A., Rega, Davide, Van Speybroeck, Veronique, Rogge, Sven M. J., Lamaire, Aran, Walton, Krista S., Bingel, Lukas W., Wuttke, Stefan, Andreo, Jacopo, Yaghi, Omar, Zhang, Bing, Yavuz, Cafer T., Nguyen, Thien S., Zamora, Felix, Montoro, Carmen, Zhou, Hongcai, Kirchon, Angelo, Fairen-Jimenez, David, College of Engineering, Department of Chemical and Biological Engineering, UAM. Departamento de Química Inorgánica, Fairen-Jimenez, David [0000-0002-5013-1194], and Apollo - University of Cambridge Repository

Subjects
Surface (mathematics), Technology, Chemistry, Multidisciplinary, Surface area, 02 engineering and technology, 01 natural sciences, GAS-STORAGE, Surface Area Analysis, General Materials Science, Porous materials, QD, BET theory, Chemistry, Physical, Nanoporous, Physics, 1. No poverty, Química, [CHIM.MATE]Chemical Sciences/Material chemistry, 3rd-DAS, Reproducibilities, 021001 nanoscience & nanotechnology, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemistry, Physics, Condensed Matter, Mechanics of Materials, Physical Sciences, Science & Technology - Other Topics, 0210 nano-technology, Porosity, Materials Science, APPLICABILITY, Materials Science, Multidisciplinary, Nanotechnology, 010402 general chemistry, Physics, Applied, METAL-ORGANIC FRAMEWORKS, Adsorption, Porosimetry, [CHIM]Chemical Sciences, ddc:530, Nanoscience & Nanotechnology, MCC, Química Inorgánica, Science & Technology, Mechanical Engineering, Science and technology, Reproducibility of Results, QD Chemistry, 0104 chemical sciences, Physics and Astronomy, Brunauer Emmett Tellers
Abstract

This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (NanoMOFdeli), ERC-2016-COG 726380, Innovate UK (104384) and EPSRC IAA (IAA/RG85685). N.R. acknowledges the support of the Cambridge International Scholarship and the TrinityHenry Barlow Scholarship (Honorary). O.K.F. and R.Q.S. acknowledge funding from the U.S. Department of Energy (DE-FG02-08ER15967). R.S.F. and D.B. acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (SCoTMOF), ERC-2015-StG 677289. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA-0003525. The authors gratefully acknowledge funding from the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, through the Hydrogen Storage Materials Advanced Research Consortium (HyMARC). This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. J.D.E. acknowledges the support of the Alexander von Humboldt Foundation and the Center for Information Services and High Performance Computing (ZIH) at TU Dresden. S.K.G. and S.M. acknowledge SERB (Project No. CRG/2019/000906), India for financial support. K.K. and R.K. acknowledge Active Co. Research Grant for funding. S.K. acknowledges funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (COSMOS), ERC-2017-StG 756489. N.L. and J.G.M acknowledge funding from the European Commission through the H2020-MSCA-RISE-2019 program (ZEOBIOCHEM -872102) and the Spanish MICINN and AEI/FEDER (RTI2018-099504-B-C21). N.L. thanks the University of Alicante for funding (UATALENTO17-05). ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV-2017-0706) S.M.J.R. and A.L. wish to thank the Fund for Scientific Research Flanders (FWO), under grant nos. 12T3519N and 11D2220N. L.S. was supported by the EPSRC Cambridge NanoDTC EP/L015978/1. C.T.Y. and T.S.N. acknowledges funds from the National Research Foundation of Korea, NRF-2017M3A7B4042140 and NRF-2017M3A7B4042235. P.F. and H. Y. acknowledge US Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under Award No. DE-SC0010596 (P.F.). R.O. would like to acknowledge funding support during his Ph.D. study from Indonesian Endowment Fund for Education-LPDP with the contract No. 202002220216006. Daniel Siderius: Official contribution of the National Institute of Standards and Technology (NIST), not subject to copyright in the United States of America. Daniel Siderius: Certain commercially available items may be identified in this paper. This identification does not imply recommendation by NIST, nor does it imply that it is the best available for the purposes described. B.V.L, S.T.E and A.M.P acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Program (Grant agreement no. 639233, COFLeaf)., Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of microand mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This roundrobin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible., European Research Council (ERC) ERC-2016-COG 726380 ERC-2015-StG 677289 ERC-2017-StG 756489 639233, UK Research & Innovation (UKRI) Innovate UK 104384 UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) IAA/RG85685, Cambridge International Scholarship TrinityHenry Barlow Scholarship, United States Department of Energy (DOE) DE-FG02-08ER15967, National Nuclear Security Administration DE-NA-0003525, United States Department of Energy (DOE), Alexander von Humboldt Foundation, Center for Information Services and High Performance Computing (ZIH) at TU Dresden, Department of Science & Technology (India), Science Engineering Research Board (SERB), India CRG/2019/000906, Active Co. Research Grant, European Commission through the H2020-MSCA-RISE-2019 program ZEOBIOCHEM -872102, Spanish MICINN and AEI/FEDER RTI2018-099504-B-C21, University of Alicante UATALENTO17-05, Spanish Government SEV-2017-0706 FWO 12T3519N 11D2220N, UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) EP/L015978/1, National Research Foundation of Korea NRF-2017M3A7B4042140 NRF-2017M3A7B4042235, United States Department of Energy (DOE) DE-SC0010596, Indonesian Endowment Fund for Education-LPDP 202002220216006

Published
2022

39. Mathematical Modeling of Energy-Dense NMC Electrodes: I. Determination of Input Parameters

Author

Tuan-Tu Nguyen, Bruno Delobel, Maxime Berthe, Benoît Fleutot, Arnaud Demortière, Charles Delacourt, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Technocentre Renault [Guyancourt], RENAULT, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Plateforme de Caractérisation Multi-Physiques - IEMN (PCMP - IEMN), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The authors would like to acknowledge French National Association for Research and Technology (ANRT) for partially supporting the funding of this research work. T.T. Nguyen was supported by Renault Group for his PhD Project. This work has been supported by the IEMN-PCMP-PCP platform and by the RENATECH network., PCMP PCP, Renatech Network, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 [LRCS], Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 [IEMN], Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
[SPI]Engineering Sciences [physics], [CHIM.GENI]Chemical Sciences/Chemical engineering, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Renewable Energy, Sustainability and the Environment, Physics::Plasma Physics, Materials Chemistry, Electrochemistry, Condensed Matter Physics, [SPI.MAT]Engineering Sciences [physics]/Materials, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract

Physics-based models of the Li-ion battery are promising to decipher and quantify the electrode limitations, thereby providing valuable insights for choosing the optimal electrode design for a specific application. However, to obtain relevant results from the models, a reliable set of input parameters is required. This work presents a combined experimental/modeling approach relying on the Newman pseudo-2D model for a complete characterization of a set of LiNi0.5Mn0.3Co0.2O2 electrodes. Intrinsic properties of the active materials are determined and validated using low-loading electrodes having negligible porous-electrode limitations. Then, high-energy-density electrode properties are characterized using appropriate experimental methods, which are widely reported in the literature. In the second part of this series of papers, parameters obtained from this part serve as input parameters in the Newman pseudo-2D model as well as in its extension in order to simulate the rate capability during discharge of the aforementioned set of high-energy-density electrodes. List of symbols a i m i 2 / m PE 3 interfacial surface area of phase i c s , surf mol m − 3 concentration at the surface of the AM particle c s , max mol m − 3 maximum concentration of intercalated Li in AM particle c s mol m − 3 solid-phase Li concentration within the AM particle c ¯ s mol m − 3 local volume-averaged solid Li concentration of AM phase within the PA c mol m − 3 salt concentration in a binary electrolyte d 50 μ m median diameter of AM particles D m 2 s − 1 bulk diffusion coefficient of the liquid phase D s m 2 s − 1 diffusion coefficient of Li in the AM particles F C mol − 1 Faraday’s constant i coexisting phase presented in the PE i n 0 A m − 2 exchange current density i Li 0 A m − 2 exchange current density at the Li foil I app A / m CC 2 discharge current density j n mol / m AM 2 · s pore-wall flux across the sandwich k 0 mol m 2 · s · mol m − 3 1.5 − 1 reaction rate constant of the AM k 0 , Li mol m 2 · s · mol m − 3 0.5 − 1 reaction rate constant of Li foil L el μ m PE thickness L sep μ m separator thickness Q th Ah kg − 1 electrode theoretical capacity R J mol · K − 1 ideal gas constant r μ m radial dimension along the AM particle T K absolute temperature t s time t + 0 transference number of Li+ in the electrolyte with respect to the solvent velocity U V equilibrium potential of the AM Δ V V voltage drop between the two inner contacts in the μ4-probe experiment x μ m dimension across the sandwich x 0 initial stoichiometry Greek Symbols α thermodynamic factor β charge transfer coefficient ε m elyte 3 / m PE 3 PE porosity ε sep m elyte 3 / m sep 3 separator porosity κ eff S m − 1 effective ionic conductivity of the liquid phase ρ el g cm − 3 electrode density σ eff S m − 1 effective electronic conductivity of the solid phase of the electrode τ Br tortuosity factor by Bruggeman τ e electrode tortuosity factor τ sep tortuosity factor of the separator Φ 1 , Li V electric potential at Li foil Φ i V electric potential of phase i

Published
2022

40. Functional nanoporous materials from boronate-containing stimuli-responsive diblock copolymers

Author

Erigene Bakangura, David Fournier, Fanny Coumes, Patrice Woisel, Daniel Grande, Benjamin Le Droumaguet, Unité Matériaux et Transformations - UMR 8207 (UMET), Institut National de la Recherche Agronomique (INRA)-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
inorganic chemicals, boronate ester, [CHIM.POLY]Chemical Sciences/Polymers, Polymers and Plastics, cleavable junction, Organic Chemistry, technology, industry, and agriculture, Bioengineering, [CHIM.MATE]Chemical Sciences/Material chemistry, diblock copolymers, Biochemistry, nanoporous polymers
Abstract

International audience; Functional nanoporous polymeric materials have been prepared from novel polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer precursors containing a reversible boronate ester junction between both blocks. To this purpose, homopolymers presenting either a boronic acid or a (nitro)catechol end functionality were synthesized. The coupling of each homopolymer presenting complementary chemical functions was successfully achieved under mild conditions and allowed for the generation of the corresponding boronate ester-containing diblock copolymers. Upon orientation of these precursors on silicon wafers via solvent vapor annealing, the resulting films were submitted to PEO etching through selective cleavage of the boronate ester junction under mild acidic conditions. SEM micrographs of the as-obtained thin films revealed the generation of 12 nm-diameter oriented cylindrical nanopores perpendicular to the silicon support surface.

Published
2022

41. Enhanced passivity of Cr-Fe-Co-Ni-Mo multi-component single-phase face-centred cubic alloys: design, production and corrosion behaviour

Author

Wang, Xueying, Mercier, Dimitri, Danard, Yolande, Rieger, Thomas, Perrière, Loïc, Laurent-Brocq, Mathilde, Guillot, Ivan, Maurice, Vincent, Marcus, Philippe, Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), European Project: 741123,CIMNAS, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC)

Subjects
General Chemical Engineering, microstructure, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], pitting corrosion, General Materials Science, passivity, General Chemistry, production, [CHIM.MATE]Chemical Sciences/Material chemistry, Multi-principal element alloys, thermodynamic diagrams
Abstract

The vast composition space of the Cr-Fe-Co-Ni-Mo system was explored by massive thermodynamic calculations in order to design and characterize multi-component single-phase fcc alloys optimized in Cr and Mo content and having enhanced passivity. Adding up to 15 at.% Mo while retaining the fcc single-phase is possible, which is unprecedented. Cr is confirmed to be a prerequisite to ensure self-protection against corrosion by passivation. Adding Mo up to 10 at.% tremendously enhances the resistance to passivity breakdown in Cl--containing aggressive environment. Newly designed quinary alloys, Cr25Fe25Co5Ni40Mo5 and Cr15Fe10Co5Ni60Mo10 (at.%), show superior resistance to localized corrosion.

Published
2022

42. Fluorogenic Protein Probes with Red and Near‐Infrared Emission for Genetically Targeted Imaging**

Author

Blaise Dumat, Nicolas Pietrancosta, Sylvestre P. J. T. Bachollet, Cyril Addi, Jean-Maurice Mallet, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), and ANR-18-CE44-0006,DIPimaging,Sondes fluorogéniques à double détection pour l'imagerie biphotonique localisée(2018)

Subjects
Diagnostic Imaging, Infrared Rays, Quantum yield, Molecular Dynamics Simulation, Conjugated system, Ligands, 010402 general chemistry, 01 natural sciences, Fluorescence, Catalysis, Humans, [CHIM]Chemical Sciences, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Fluorescent Dyes, High contrast, 010405 organic chemistry, Chemistry, Organic Chemistry, Near-infrared spectroscopy, Proteins, General Chemistry, Ligand (biochemistry), Fusion protein, In vitro, 0104 chemical sciences, [SDV.BBM.BP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, HEK293 Cells, Biophysics, HeLa Cells
Abstract

International audience; Fluorogenic probes are important tools to image proteins with high contrast and no wash protocols. In this work, we rationally designed and synthesized a small set of four protein fluorogens with red or near-infrared emission. The fluorophores were characterized in the presence of albumin as a model protein environment and exhibited good fluorogenicity and brightness (fluorescence quantum yield up to 36 %). Once conjugated to a haloalkane ligand, the probes reacted with the protein self-labeling tag HaloTag with a high fluorescence enhancement (up to 156-fold). The spectroscopic properties of the fluorogens and their reaction with HaloTag were investigated in vitro experimentally and with the help of molecular dynamics. The two most promising probes, one in the red and one in the near-infrared range, were finally applied to image the nucleus or actin in live-cell and in wash-free conditions using fluorogenic and chemogenetic targeting of HaloTag fusion proteins.

Published
2020

43. Enumeration as a Tool for Structure Solution: A Materials Genomic Approach to Solving the Cation-Ordered Structure of Na3V2(PO4)2F3

Author

Gerard S. Mattei, Peter G. Khalifah, Christian Masquelier, Emmanuelle Suard, Anubhav Jain, Laurence Croguennec, John Dagdelen, Matteo Bianchini, Alex M. Ganose, Kristin A. Persson, François Fauth, Gerbrand Ceder, Department of Chemistry, Stony Brook University [SUNY] (SBU), State University of New York (SUNY)-State University of New York (SUNY), Brookhaven National Laboratory [Upton, NY] (BNL), U.S. Department of Energy [Washington] (DOE)-UT-Battelle, LLC-Stony Brook University [SUNY] (SBU), Lawrence Berkeley National Laboratory [Berkeley] (LBNL), Department of Materials Science and Engineering, University of California [Berkeley], University of California-University of California, Institut Laue-Langevin (ILL), ILL, ALBA Synchrotron light source [Barcelone], Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This work was intellectually led and supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract no. DE-SC0012704 and DE-AC02–05CH11231 (Materials Project program KC23MP) at BNL and LBNL, respectively. The Institute Laue-Langevin (ILL) is acknowledged for funding the Ph.D. thesis of MB. The ALBA synchrotron and the MSPD beamline are acknowledged for providing in-house beamtime. We gratefully acknowledge discussion with Nils Zimmerman (LBNL), Branton Campbell (BYU), and Alan Coelho (Coelho software) about other types of analysis approaches that were tested but were not reported here, and discussions with John Evans (Durham) about prior work on structure solution for extremely large crystal structures using powder diffraction data., UT-Battelle, LLC-Stony Brook University [SUNY] (SBU), State University of New York (SUNY)-State University of New York (SUNY)-U.S. Department of Energy [Washington] (DOE), University of California [Berkeley] (UC Berkeley), University of California (UC)-University of California (UC), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Materials science, General Chemical Engineering, Structure (category theory), [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Crystallography, Engineering, Chemical Sciences, Materials Chemistry, Enumeration, 0210 nano-technology, Materials, Powder diffraction
Abstract

International audience; While powder diffraction methods are routinely utilized to optimize structural models for compounds whose crystal structures are known, the determination of unknown structures is far more challenging. When the unknown structure is large, structure solution can become a virtually intractable problem using standard structure solution methodologies, especially when the space group cannot be unambiguously resolved. One such system is the promising Na-ion battery cathode material Na3V2(PO4)2F3 whose high temperature and room temperature structures were previously solved, but whose more complex low-temperature structure could not be determined. Here, a novel materials genomic approach is demonstrated for the solution of the unknown 100 K structure of Na3V2(PO4)2F3 in which enumeration methods are first used to generate a large number (~3,000) of trial structures based on plausible orderings of Na ions and then automated Rietveld refinements are carried out to optimize each of these trial structures. Based on both the analysis of the ensemble of optimized trial structures and the density functional theory energy minimization of selected trial structures, the 100 K structure of Na3V2(PO4)2F3 is best described as belonging to the space group A21am with unit cell dimensions of a = 9.01928(4), b = 27.1379(1), c = 10.73307(5). The 100 K unit cell has a large volume of 2627.07(2) Å3 with Z = 12 and 33 independent crystallographic sites (9 Na, 3 V, 3 P, 12 O, and 6 F) that is 3x and 6x larger than the room- and high-temperature polymorphs of this phase, respectively. The novel methods described here will be generally applicable for the solution of the complex cation-ordered structures that commonly occur for battery materials.

Published
2020

44. Analyses non invasives in situ des œuvres préhistoriques de la grotte de Font-de-Gaume pour une meilleure connaissance du décor pariétal polychrome et de son organisation

Author

Ina Reiche, Antoine Trosseau, Katharina Müller, Marine Gay, David Strivay, Jean-Jacques Cleyet-Merle, Rathgen-Forschungslabor, Staatliche Museen zu Berlin-Stiftung Preußischer KulturbesitzBerlin, Delft University of Technology (TU Delft), Laboratoire d'Archéologie Moléculaire et Structurale (LAMS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche de Chimie Paris (IRCP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), Université de Liège, musée national de Préhistoire des Eyzies, Ministère de la Culture (MC), and Rathgen-Forschungslabor

Subjects
0106 biological sciences, art pariétal des grottes ornées, 010506 paleontology, [SHS.ARCHEO]Humanities and Social Sciences/Archaeology and Prehistory, iron oxides, oxydes de fer, manganese oxides, General Engineering, portable X-ray fluorescence, 010603 evolutionary biology, 01 natural sciences, painted cave art, oxydes de manganèse, fluorescence X portable, traitement quantitatif des données, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, analyse non-invasive, polychrome paints, non-invasive analysis, peintures polychromes, quantitative data processing, 0105 earth and related environmental sciences
Abstract

International audience; In this article we present a first assessment of recent results of chemical analysis of the decor of the Font-de Gaume cave. These data were obtained during four field missions between 2013 and 2017. Slightly more than two hundred representations are divided between animal art and signs (tectiforms), in proportions of about two thirds to one third. Most represented is the bison, hence the name "Bison Cave". The figures were made with different techniques. We find polychrome paintings, drawings and engravings. The state of conservation of the cave is a reflection of its great fragility. The walls are very heterogeneous, which represents a real analytical challenge for the chemical analysis of figures since the analyzes must be lim-ited to non-invasive approaches without contact. Thus, we carried out around two hundred analyzes by portable X-ray fluorescence to characterize the coloring matters. These analyzes were carried out in order to obtain new elements of answer as for the chemical composition of the coloring matter used and the techniques of realization of these works of the Upper Paleolithic. Here we present the approach used, focusing particularly on the processing of the measurements carried out. These first evaluations of the data made it possible to identify dif-ferent coloring materials used in the Font-de-Gaume cave. The approach developed has thus shown its potential, when applying on a larger number of figures and by integrating additional information. In the long term this enables improving knowledge of these works and their suc-cessive realization in the case of superimposed figures which seems very important, in the absence of a direct dating of the parietal works of Font-de-Gaume.; Dans cet article est présenté un premier bilan des résultats récents d’analyse chimiques du décor de la grotte de Font-de Gaume. Ces données ont été obtenues lors de quatre missions de terrain entre 2013 et 2017. Un peu plus de deux cents représentations se répartissent entre un art animalier et des signes (tectiformes), dans des proportions d’environ deux tiers un tiers. L'animal le plus représenté est le bison, d'où le nom la "Caverne des bisons". Les figures ont été réalisées avec différentes techniques. On retrouve la peinture polychrome, le dessin et les gravures. L’état de conservation de la grotte étant le reflet de sa grande fragilité, les parois sont très hétérogènes, ce qui représente un réel défi analytique pour l’analyse chimique des figures dans la mesure où les analyses doivent se limiter à des approches non invasives sans contact. Ainsi, nous avons réalisé environ deux cents analyses par fluorescence X portable pour caractériser les matières colorantes. Ces analyses ont été effectuées dans le but d'obte-nir de nouveaux éléments de réponse quant à la composition chimique de la matière colo-rante utilisée et les techniques de réalisation de ces œuvres du Paléolithique supérieur. Nous présentons ici l'approche utilisée en se focalisant particulièrement sur les traitements des me-sures effectuées. Ces premières évaluations des données ont permis d'identifier différentes matières colorantes utilisées dans la grotte de Font-de Gaume. L'approche développée a ainsi montré son potentiel, lorsqu'elle sera utilisée sur un plus grand nombre de figures et en inté-grant d’autres informations complémentaires. Elle devrait permettre à terme d’améliorer la connaissance de ces œuvres et de leur réalisation successive dans le cas de superpositions des figures ce qui parait très important, en l’absence d’une datation directe des œuvres parié-tales de Font-de-Gaume.

Published
2020

45. A DFT Protocol for the Prediction of 31P NMR Chemical Shifts of Phosphine Ligands in First-Row Transition-Metal Complexes

Author

Luca Alessandro Perego, Ilaria Ciofini, Laurence Grimaud, Pierre-Adrien Payard, Laboratoire des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institute of Chemistry for Life and Health Sciences (iCLeHS), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemical shift, Organic Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Transition metal, chemistry, Computational chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Phosphine
Abstract

International audience; While 31P NMR is a major technique to characterize phosphine-ligated transition-metal complexes—which are ubiquitous in catalysis—31P NMR chemical shifts are difficult to predict using empirical rules or tabulated data. Aiming at filling this gap, we propose here guidelines enabling their prediction at a modest computational cost. Rooted in density functional theory, our protocol features structural optimization and magnetic shielding tensor calculations performed at a global hybrid level using a tailored locally dense basis set. Validation on an experimental data series revealed that while a careful conformational analysis is required in the case of flexible phosphines, the use of the free ligand or another complex as a reference for chemical shifts often allows solving this drawback. Applicability to various diamagnetic complexes of first-row transition metals is demonstrated, including large systems relevant to contemporary catalysis.

Published
2020

46. Multivalent Mg2+-, Zn2+-, and Ca2+-Ion Intercalation Chemistry in a Disordered Layered Structure

Author

Jiwei Ma, Kyle G. Reeves, Seongkoo Kang, Alexandre Ponrouch, Olaf J. Borkiewicz, Damien Dambournet, Toshinari Koketsu, Peter Strasser, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Technical University of Berlin / Technische Universität Berlin (TU), Tongji University, Argonne National Laboratory [Lemont] (ANL), Institut de Ciència de Materials de Barcelona (ICMAB), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Consejo Superior de Investigaciones Científicas [Spain] (CSIC), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Technical University Berlin, Agence Nationale de la Recherche (France), European Research Council, Department of Energy (US), and Ministerio de Economía, Industria y Competitividad (España)

Subjects
Intercalation (chemistry), Energy Engineering and Power Technology, 02 engineering and technology, engineering.material, Perovskite, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Layered structure, Multivalent, Materials Chemistry, Electrochemistry, [CHIM]Chemical Sciences, Chemical Engineering (miscellaneous), Electrical and Electronic Engineering, Lepidocrocite, Ion intercalation, Perovskite (structure), Electrode material, Chemistry, Rechargeable batteries, 021001 nanoscience & nanotechnology, 3. Good health, 0104 chemical sciences, Chemical engineering, engineering, Defects, 0210 nano-technology, Disordered structure
Abstract

The development of practical multivalent-ion batteries critically depends on the identification of suitable positive electrode materials. To gain a better understanding of the intercalation chemistry of multivalent ions, model frameworks can be used to study the distinct specificities of possible multivalent ions, thus expanding our knowledge on the emerging “beyond Li battery” technology. Here, we compare the intercalation chemistry of Mg2+, Zn2+, and Ca2+ ions in a disordered layered-type structure featuring water interlayers and cationic vacancies as possible host sites. The thermodynamics of cation-inserted reactions performed on the model structure indicated that these reactions are thermodynamically favorable with Zn2+ being the least stable ion. Galvanostatic measurements confirmed that the structure is inactive toward Zn2+ intercalation, while Mg2+ can be reversibly inserted (0.37 Mg2+ per formula unit) with minor changes in the atomic arrangement, as demonstrated by pair distribution function analysis. Moreover, we demonstrate that nonsolvated Mg2+ was intercalated in the structure. Finally, the intercalation of Ca2+ performed at 100 °C with Ca(BF4)2 in propylene carbonate induced the collapse of the layered structure releasing water molecules that contribute to the degradation of the electrolyte, as revealed by the presence of CaF2 at the electrode level. The decomposition of the structure led to the formation of an electrochemically active phase featuring a strong long-range disorder, yet a short-range order close to that found in perovskite structures, particularly with corner-shared TiO6 octahedra. We, hence, hypothesize that defective CaTiO3-based perovskite could be explored as viable cathode materials for rechargeable Ca-based batteries., The research leading to these results received funding from the French National Research Agency under Idex@Sorbonne University for the Future Investments Program (no. ANR-11-IDEX-0004-02). Funding from the European Union’s Horizon 2020 research is acknowledged: European Research Council (ERC-2016-STG, CAMBAT grant agreement no. 715087). The work done at the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under contract no. DE-AC02-06CH11357. A.P. is grateful to the Spanish Ministry for Economy, Industry and Competitiveness Severo Ochoa Programme for Centres of Excellence in R&D (SEV-2015-0496). We thank IMPC FR2482 for SEM-FEG and TEM instrumentation funded by CNRS, Sorbonne Université and C’Nano projets of Region Ile-de-France.

Published
2020

47. Pressure‐Induced Conversion of a Paramagnetic FeCo Complex into a Molecular Magnetic Switch with Tuneable Hysteresis

Author

Amina Benchohra, Ludovic Delbes, Keevin Béneut, Alain Soyer, Yanling Li, Kamel Boukheddaden, Paraskevas Parisiades, Benoit Baptiste, Rodrigue Lescouëzec, Buqin Xu, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Groupe d'Etude de la Matière Condensée (GEMAC), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Molecular switch, Materials science, Bistability, 010405 organic chemistry, Magnetism, Intermolecular force, charge transfer, cyanides, General Medicine, General Chemistry, Magnetic switch, 010402 general chemistry, Magnetic hysteresis, 01 natural sciences, Catalysis, 0104 chemical sciences, Paramagnetism, Hysteresis, Chemical physics, magnetism, coordination chemistry, [CHIM]Chemical Sciences, molecular switches
Abstract

International audience; A key challenge in the design of magnetic molecular switches is to obtain bistability at room temperature. Here, we show that application of moderate pressure makes it possible to convert a paramagnetic FeIII2CoII2 square complex into a molecular switch exhibiting a full dia‐ to paramagnetic transition: FeIICoIII ⇔ FeIIICoII. Moreover, the complex follows a rare behavior: the higher the pressure, the broader the magnetic hysteresis. Thus, the application of an adequate pressure allows inducing a magnetic bistability at room temperature with predictable hysteresis width. The structural studies at different pressures suggest that the pressure‐enhanced bistability is due to the strengthening of intermolecular interactions upon pressure increase. An original microscopic Ising‐like model including pressure effects is developed to simulate this unprecedented behavior. Overall, this study shows that FeCo complexes could be very sensitive piezo switches with potential use as sensors.

Published
2020

48. Simple Parameter-Free Bridge Functionals for Molecular Density Functional Theory. Application to Hydrophobic Solvation

Author

Guillaume Jeanmairet, Sohvi Luukkonen, Daniel Borgis, Luc Belloni, Maison de la Simulation (MDLS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut National de Recherche en Informatique et en Automatique (Inria)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Physics, Quantitative Biology::Biomolecules, 010304 chemical physics, Monte Carlo method, Solvation, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Integral equation, 0104 chemical sciences, Surfaces, Coatings and Films, Hydrophobic effect, Surface tension, Cavitation, 0103 physical sciences, Materials Chemistry, Compressibility, Molecular Density, Statistical physics, Physical and Theoretical Chemistry
Abstract

International audience; Computer simulations have been substantial in understanding the fine details of hydrophobic solvation and hydrophobic interactions. Alternative approaches based on liquid-state theories have been proposed, but are not yet at the same degree of completeness and accuracy. In this vein, a classical, molecular density functional theory approach to hydrophobic solvation is introduced. The lowest, second-order approximation of the theory, equivalent to the hypernetted chain approximation in integral equations, fails in describing correctly cavitation free-energies. It is corrected here by two simple, angular-independent, so-called bridge functionals; they are parameter-free in the sense that all variables can be fixed unambiguously from the water bulk properties, including pressure, isothermal compressibility, and liquid-gas surface tension. A hard-sphere bridge functional, based on the known functional of a reference hard fluid system, turns out to face strong limitations for water. A simpler weighted density approximation is shown to properly reproduce the solvation free energy of hydrophobes of various sizes, from microscopic ones to the nanoscale, and predicting the solvation free-energy of a dataset of more than 600 model hydrophobic molecules having a variety of shapes and sizes with an accuracy of a quarter of $k_BT$ compared to Monte-Carlo simulations values. It constitutes an excellent starting point for a general functional describing accurately both hydrophobic and hydrophilic solvation, and making it possible to study non-idealized hydrophobic interactions.

Published
2020

49. Mg3(BH4)4(NH2)2 as Inorganic Solid Electrolyte with High Mg2+ Ionic Conductivity

Author

Benoit Fleutot, Ronan Le Ruyet, Yaroslav Filinchuk, Raphaël Janot, Yasmine Benabed, Geoffroy Hautier, Romain Berthelot, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université Catholique de Louvain = Catholic University of Louvain (UCL), Unité de Chimie des Interfaces (UCL), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Laboratory of Chemistry and Electrochemistry of Solids, Université de Montréal (UdeM), Institut de la matière condensée et des nanosciences / Institute of Condensed Matter and Nanosciences (IMCN), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), UCL - SST/IMCN/MODL - Modelling, and UCL - SST/IMCN/MOST - Molecular Chemistry, Materials and Catalysis

Subjects
crystal structure, Materials science, Mg-ion battery, Analytical chemistry, Energy Engineering and Power Technology, 02 engineering and technology, Crystal structure, Electrolyte, 010402 general chemistry, Borohydride, 01 natural sciences, Metrics & More Article Recommendations ionic conductor, Tetragonal crystal system, chemistry.chemical_compound, borohydride, Materials Chemistry, Electrochemistry, [CHIM]Chemical Sciences, Chemical Engineering (miscellaneous), Ionic conductivity, Electrical and Electronic Engineering, ComputingMilieux_MISCELLANEOUS, Phase diagram, impedance spectroscopy, 021001 nanoscience & nanotechnology, ionic conductor, 0104 chemical sciences, Dielectric spectroscopy, chemistry, 0210 nano-technology
Abstract

International audience; Mg 3 (BH 4) 4 (NH 2) 2 compound was synthesized through the investigation of the Mg(BH 4) 2-Mg(NH 2) 2 phase diagram; its crystal structure was solved in a tetragonal unit cell with the space group I4̅. Interestingly, Mg 3 (BH 4) 4 (NH 2) 2 has a high thermal stability with a decomposition temperature above 190°C and exhibits a high Mg 2+ ionic conductivity of 4.1 × 10 −5 S•cm −1 at 100°C with a low activation energy (0.84 eV). The reversible Mg deposition/stripping was demonstrated at 100°C when using Mg 3 (BH 4) 4 (NH 2) 2 as solid electrolyte. Thus, Mg 3 (BH 4) 4 (NH 2) 2 is a compound that could help to develop rechargeable Mg-ion solid-state batteries.

Published
2020

50. Dual-Cation Electrolytes for High-Power and High-Energy LTO//AC Hybrid Capacitors

Author

Natsuki Miyashita, Wako Naoi, Yu Chikaoka, Shinichi Seto, Masato Sakurai, Patrice Simon, McMahon Thomas Homer Reid, Tsukasa Ueda, Katsuhiko Naoi, Etsuro Iwama, Tokyo University of Agriculture and Technology (TUAT), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Centre National de la Recherche Scientifique - CNRS (FRANCE), Collège de France (FRANCE), Ecole Nationale Supérieure de Chimie de Paris - ENSCP (FRANCE), Ecole Nationale Supérieure de Chimie de Montpellier - ENSCM (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Institut polytechnique de Grenoble (FRANCE), K & W Inc. (JAPAN), Sorbonne Université (FRANCE), Tokyo University of Agriculture and Technology - TUAT (JAPAN), Université Grenoble Alpes - UGA (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Université de Nantes (FRANCE), Université de Picardie Jules Verne (FRANCE), PSL Research University (FRANCE), Université de Pau et des Pays de l'Adour - UPPA (FRANCE), Université de Haute Alsace - UHA (FRANCE), Centre Interuniversitaire de Recherche et d'Ingénierie des Matériaux - CIRIMAT (Toulouse, France), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Materials science, Supporting electrolyte, Matériaux, 02 engineering and technology, Electrolyte, 010402 general chemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, law.invention, law, Physical and Theoretical Chemistry, Power density, Resistive touchscreen, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Capacitor, General Energy, Chemical engineering, Overvoltage, Electrode, 0210 nano-technology
Abstract

International audience; Dual-cation electrolyte systems, which contain two cations [Li+ and spiro-1,1′-bipyrrolidinium (SBP+), are proposed to enhance the power capability of hybrid capacitors composed of thick Li4Ti5O12 (LTO) negative (200 μm) and activated carbon (AC) positive electrodes (400 μm), which thus reduces the resistive overvoltage in the system. Detailed studies of the mass transport properties based on the combination of spectroscopy and electrochemical analysis have shown that the presence of SBP+, despite slower Li+ transport in the electrolyte bulk, further reduces overvoltage associated with migration limitation in the thick LTO electrode macropores. This study on the dual-cation electrolyte quantifies the influence of the addition of a supporting electrolyte and shows interest in SBPBF4 addition for increasing the output power density of hybrid capacitors with a thick electrode configuration.

Published
2020

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