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1. Self-identification algorithm for zeolite-based thermal capacity gas sensor

Author: Hussein Awala, S. Inoue, A. Mita-Tixier, Yoshio Mita, Didier Robbes, Svetlana Mintova, Maxime Harnois, Corentin Jorel, Mathieu Pouliquen, C. Radu, O. De Sagazan, Eric Lebrasseur, Julien Grand, Yuki Okamoto, Kentaro Yamada, Matthieu Denoual, Laboratoire d'automatique de Caen (LAC), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Equipe Electronique - Laboratoire GREYC - UMR6072, Groupe de Recherche en Informatique, Image et Instrumentation de Caen (GREYC), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Laboratory for Integrated Micro Mechatronics Systems (LIMMS), Centre National de la Recherche Scientifique (CNRS)-The University of Tokyo (UTokyo), Laboratoire catalyse et spectrochimie (LCS), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Institut d'Électronique et des Technologies du numéRique (IETR), Nantes Université (NU)-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)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), The University of Tokyo (UTokyo), Institut d'Electronique et de Télécommunications de Rennes ( IETR ), Université de Nantes ( UN ) -Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Institut National des Sciences Appliquées - Rennes ( INSA Rennes ) -CentraleSupélec-Centre National de la Recherche Scientifique ( CNRS ), Denain Anzin Minéraux, National Institute for Plasma and Radiation Physics ( NILPRP ), Centre de recherche, Groupe de Recherche en Informatique, Image, Automatique et Instrumentation de Caen ( GREYC ), Université de Caen Normandie ( UNICAEN ), Normandie Université ( NU ) -Normandie Université ( NU ) -Ecole Nationale Supérieure d'Ingénieurs de Caen ( ENSICAEN ), Normandie Université ( NU ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Caen Normandie ( UNICAEN ), Normandie Université ( NU ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire catalyse et spectrochimie ( LCS ), Franche-Comté Électronique Mécanique, Thermique et Optique - Sciences et Technologies ( FEMTO-ST ), Université de Technologie de Belfort-Montbeliard ( UTBM ) -Ecole Nationale Supérieure de Mécanique et des Microtechniques ( ENSMM ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Franche-Comté ( UFC ), Institute for Material Research ( IMR ), Tohoku University [Sendai], Institute for Solid State Physics, The University of Tokyo, Université de Nantes (UN)-Université de Rennes 1 (UR1), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS), The University of Tokyo (UTokyo)-Centre National de la Recherche Scientifique (CNRS), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), and intelligente Semiconductor Microsystem Laboratory (iSML)
Subjects: Materials science, Silicon, chemistry.chemical_element, zeolites, 02 engineering and technology, engineering.material, 01 natural sciences, Heat capacity, thermal capacity gas sensor, 010309 optics, Condensed Matter::Materials Science, Coating, 0103 physical sciences, Thermal, [ SPI ] Engineering Sciences [physics], system identification algorithm, Electrical and Electronic Engineering, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, Zeolite, ComputingMilieux_MISCELLANEOUS, [ PHYS ] Physics [physics], Atmospheric pressure, Extraction (chemistry), 021001 nanoscience & nanotechnology, Condensed Matter Physics, Microstructure, Electronic, Optical and Magnetic Materials, chemistry, Hardware and Architecture, engineering, 0210 nano-technology, Algorithm
Abstract: International audience; We demonstrate a new operation mode of thermal gas sensor based on thermal capacity extraction with identification algorithm. The system is a silicon microstructure covered with zeolites operated at constant temperature while stimulated by heat pseudo-random sequence. The proposed detection principle is demonstrated at room temperature and atmospheric pressure through the detection of gas water molecules with an hydrophilic FAU-type zeolite coating. The identification algorithm is a continuous-time closed-loop identification algorithm based on the instrumental variable principle.
Published: 2018
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2. Direct Evidence of the Role of Co or Pt, Co Single-Atom Promoters on the Performance of MoS2 Nanoclusters for the Hydrogen Evolution Reaction

Author: Luz A. Zavala, Kavita Kumar, Vincent Martin, Frédéric Maillard, Françoise Maugé, Xavier Portier, Laetitia Oliviero, Laetitia Dubau, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Electrochimie Interfaciale et Procédés (EIP), 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 ), Université Grenoble Alpes (UGA)-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 ), Université Grenoble Alpes (UGA), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), 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), 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), and ANR Carnot Energie et Systèmes de Propulsion (ESP)ANR Carnot Energies du futur (EF)
Subjects: Non-noble electrocatalyst, Hydrogen Evolution Reaction (HER), Single Atom Promoted Molybdenum Sulfides, Proton Exchange Membrane Water Electrolyzer (PEMWE), [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Durability, Catalysis
Abstract: International audience; Developing alternatives to platinum (Pt) and iridium (Ir) in proton exchange membrane water electrolyzers is crucial on the way to viable energy provision schemes. However, although it seems difficult to substitute Ir, alternatives exist for Pt at the PEMWE cathode. Here, we report on the synthesis and the characterization of efficient and durable hydrogen evolution reaction (HER) nanocatalysts based on MoS2 supported on high surface area carbon. Citric acid was used as a chelating agent to control the size of the crystallites (1.4 nm) and thus the density of active sites (slab edges). Inspired by successful approaches in catalysis for hydrodesulfurization reactions, conventional 2H MoS2 was sequentially doped with cobalt (Co) then 1 wt. % of Pt. Overpotentials of 188 mV, 140 and 118 mV at 10 mA cm-2 are reported for MoS2/C, Co-MoS2/C and Pt1%-CoMoS2/C, respectively. This result is attributed to the weakening of Hads binding energy of the promoted MoS2 edge active sites (because the promoting atoms are mostly located at the edges). Associated with small metal dissolution rates (monitored in situ, during HER), our findingsdemonstrate that metal promotion (doping) is a promising route to replace platinum by earth-abundant elements in acidic water electrolyzers.
Published: 2023
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3. Catalytic ozonation with γ-Al2O3 to enhance the degradation of refractory organics in water

Author: Hubert Debellefontaine, Julie Mendret, Frédéric Thibault-Starzyk, Hervé Leclerc, Wael Aboussaoud, Marie-Hélène Manero, Jean-Stéphane Pic, Stephan Brosillon, Karine Faucher, Anne Galarneau, Nicolas Lesage, Jullian Vittenet, Centre National de la Recherche Scientifique - CNRS (FRANCE), Ecole Nationale Supérieure d'Ingénieurs de Caen - ENSICAEN (FRANCE), Ecole Nationale Supérieure de Chimie de Montpellier - ENSCM (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Institut National de la Recherche Agronomique - INRA (FRANCE), Institut National des Sciences Appliquées de Toulouse - INSA (FRANCE), Total (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Université de Caen Basse-Normandie (FRANCE), Université de Montpellier 1 (FRANCE), Université de Montpellier 2 (FRANCE), Laboratoire Catalyse et Spectrochimie - LCS (Caen, France), 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)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Européen des membranes (IEM), Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Ingénierie des Systèmes Biologiques et des Procédés (LISBP), Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de la Recherche Agronomique (INRA), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS), Institut National Polytechnique de Toulouse - INPT (FRANCE), 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)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), French National Agency for Research (ANR) through convention ANR ECOTECH project PETZECO [1081C0230/ANR-10-ECOT-011-03], ANR-10-ECOT-0011,PETZECO(2010), 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), Institut National de la Recherche Agronomique (INRA)-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)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT), and Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Formic acid, Oxalic acid, 02 engineering and technology, Wastewater treatment, 010501 environmental sciences, Advanced oxidation process, 01 natural sciences, Catalysis, chemistry.chemical_compound, Acetic acid, Adsorption, [CHIM.GENI]Chemical Sciences/Chemical engineering, Al2O3, Organic chemistry, Phenol, Génie chimique, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Lewis acids and bases, Génie des procédés, 0105 earth and related environmental sciences, Chemistry, Process Chemistry and Technology, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, 6. Clean water, 13. Climate action, Catalytic ozonation, 0210 nano-technology, Nuclear chemistry
Abstract: International audience; Nowadays, heterogeneous catalytic ozonation appears as a promising way to treat industrial wastewaters containing refractory pollutants, which resist to biological treatments. Several oxides and minerals have been used and their behavior is subject to controversy with particularly the role of Lewis acid sites and/or basic sites and the effect of salts. In this study, millimetric mesoporous γ-Al2O3 particles suitable for industrial processes were used for enhancing the ozonation efficiency of petrochemical effluents without pH adjustment. A phenol (2,4-dimethylphenol (2,4-DMP)) was first chosen as petrochemical refractory molecule to evaluate the influence of alumina in ozonation. Single ozonation and ozonation in presence of γ-Al2O3 led to the disappearance of 2,4-DMP in 25 min and a decrease in pH from 4.5 to 2.5. No adsorption of 2,4-DMP occurred on γ-Al2O3. Adding γ-Al2O3 in the process resulted in an increase of the 2,4–DMP oxidation level. Indeed, the total organic carbon (TOC) removal was 14% for a single ozonation and 46% for ozonation with γ-Al2O3. Similarly, chemical oxygen demand (COD) removal increases from 35 to 75%, respectively. Various oxidized by-products were produced during the degradation of 2,4-DMP, but after 5 h ozonation 90% of organic by-products were acetic acid > formic acid ≫ oxalic acid. Some of the carboxylic acids were adsorbed on γ-Al2O3. The use of radical scavengers (tert-butanol) highlighted the involvement of hydroxyl radicals during catalytic ozonation with γ-Al2O3 in contrary to single ozonation, which mainly involved direct ozone reaction. γ-Al2O3 is an amphoteric solid with Lewis acid AlOH(H+) sites and basicAl-OH sites. After ozonation the amount of basic sites decreased due to carboxylates adsorption, while the Lewis acid sites remained constant as evidenced by FTIR. Several ozonation runs with γ-Al2O3 reported a progressive decrease of its catalytic activity due to the cumulative sorption of carboxylates on the basic sites. After 80 h of ozonation, a calcination at 550 °C allowed to recover allAl-OH basic sites and the initial activity of γ-Al2O3. A synthetic petrochemical effluent containing various petrochemicals (phenol, acetic acid, naphtenic acid, pyrene, naphtalene) was then treated with γ-Al2O3 with and without NaCl. Sodium ions prevented carboxylates adsorption on γ-Al2O3 leading to a higher efficiency of γ-Al2O3 in presence of NaCl and allowed to decrease the toxicity of the petrochemical effluent.
Published: 2015
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4. Selective Photocatalytic Dehydrogenation of Formic Acid by an In Situ-Restructured Copper-Postmetalated Metal–Organic Framework under Visible Light

Author: Houeida Issa Hamoud, Patrick Damacet, Dong Fan, Nisrine Assaad, Oleg I. Lebedev, Anna Krystianiak, Abdelaziz Gouda, Olivier Heintz, Marco Daturi, Guillaume Maurin, Mohamad Hmadeh, Mohamad El-Roz, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), American University of Beirut [Beyrouth] (AUB), 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), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB), Université de Technologie de Belfort-Montbeliard (UTBM)-Université de Bourgogne (UB)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre National de la Recherche Scientifique (CNRS), and University of Toronto
Subjects: Colloid and Surface Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Operando FTIR, Formic acid, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Photocatalysis, Biochemistry, MOFs, Copper, Catalysis, Hydrogen
Abstract: International audience; Formic acid is considered as one of the most promising liquid organic hydrogen carriers (LOHC). Its catalytic dehydrogenation processes generally suffer from low activity, low reaction selectivity, low stability of the catalysts and/or the use of noble-metal based catalysts. Herein, we report a highly selective, efficient, and noble metal-free photocatalyst for the dehydrogenation of formic acid. This catalyst is built from a post-metalation of a carboxylic-functionalized Zr-MOF by copper, namely UiO-66(COOH)2-Cu. The visible light driven photocatalytic dehydrogenation process through the release of hydrogen and carbon dioxide is monitored in real-time via operando FTIR and reveals almost 100% of selectivity with high stability (over 3 days) and conversion yield exceeding 60% (around 5 mmol.g-1 cat.h-1) at ambient conditions. These performance indicators make UiO-66(COOH)2-Cu among the top photocatalysts for formic acid dehydrogenation. Interestingly, the as-prepared UiO-66(COOH)2-Cu hetero-nanostructure was found moderately active under solar irradiation during an induction phase, whereupon it undergoes an in-situ restructuring process through intra-framework cross-linking with the formation of the anhydride analogue structure, UiO-66(COO)2-Cu, and nano-clustering of highly active and stable copper sites as evidenced by the operando studies coupled with steady state isotopic transient kinetic (SSITKA) experiment, TEM, XPS analysis and DFT calculations. Beyond revealing outstanding catalytic performance for UiO-66(COO)2-Cu, this work delivers an in-depth understanding of the photocatalytic reaction mechanism implying an evolutive behavior of the post-metalated copper as well as the MOF framework over the reaction. These key findings pave the ways towards the engineering of new simple and efficient catalysts for photocatalytic dehydrogenation of formic acid.
Published: 2022
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5. Passivated Surface of High Aluminum Containing ZSM-5 by Silicalite-1: Synthesis and Application in Dehydration Reaction

Author: Girolamo Giordano, Massimo Migliori, Giorgia Ferrarelli, Gianfranco Giorgianni, Francesco Dalena, Peng Peng, Maxime Debost, Philippe Boullay, Zhen Liu, Hailing Guo, Zi-Feng Yan, Svetlana Mintova, Università della Calabria [Arcavacata di Rende] (Unical), Chinese Academy of Sciences [Beijing] (CAS), Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), The Chinese University of Hong Kong [Hong Kong], and China University of Petroleum
Subjects: Renewable Energy, Sustainability and the Environment, General Chemical Engineering, [CHIM]Chemical Sciences, Environmental Chemistry, General Chemistry
Abstract: International audience
Published: 2022
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6. Ultrafast formation of exciplex species in dicyanoanthracene ZSM-5 revealed by transient emission and vibrational spectroscopy

Author: Lucie Duplouy, Matthieu Hureau, Aurélien Moncomble, Svetlana Mintova, Olivier Gardoll, Alain Moissette, Vincent De Waele, 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), Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Physics and Astronomy, General Materials Science, Physical and Theoretical Chemistry
Abstract: International audience; The photo-physical properties of dicyanoanthracene (DCA) molecules adsorbed on the external surface of ZSM-5 zeolite, forming DCA@ZSM-5 composites, have been investigated by picosecond transient emission, femtosecond transient absorption infrared vibrational spectroscopy, steady-state UV–vis, and quantum chemistry calculations. Following the photoexcitation at 420 nm of DCA@ZSM-5, the formation of the localized, LE, excited S1 state of DCA emitting below 500 nm is observed. LE is rapidly and quasi-exclusively converted into two distinct exciplex species, EX1 and EX2, detected by their emission above 520 nm, with a lifetime of 5 ns and 20 ns, respectively. The different transient species can be identified by the frequency of the CN stretching vibration that is a marker of the charge delocalisation and that is peaking respectively at 2162 (LE), 2174 (EX1) and 2187 (EX2) cm−1. DFT and TD-DFT calculations further support the assignment. The results show that the external surface of zeolite is an appropriate playground for the development of novel photoactive host–guest materials.
Published: 2023
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7. H$_2$ production from formic acid over highly stable and efficient Cu-Fe-O spinel based photocatalysts under flow, visible-light and at room temperature conditions

Author: Hanen Abdelli, Houeida Issa Hamoud, Juan Pablo Bolletta, Arnold Paecklar, Afrah Bardaoui, Krassimir L. Kostov, Ewelina Szaniawska, Antoine Maignan, Christine Martin, Mohamad El-Roz, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de nanomatériaux et des systèmes pour les énergies renouvelables [Tunis] (LANSER), Université de Tunis El Manar (UTM), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Charles University [Prague] (CU), and ANR-10-LABX-0009,EMC3,Energy Materials and Clean Combustion Center(2010)
Subjects: LOHC, [CHIM]Chemical Sciences, General Materials Science, Photocatalysis Hydrogen LOHC Formic acid Dehydrogenation, Formic acid, Dehydrogenation, Photocatalysis, Hydrogen
Abstract: International audience; Catalytic dehydrogenation of liquid organic hydrogen carriers (LOHC), such as formic acid (FAc), is considered as a promising approach to safely store and easily transport hydrogen at ambient conditions. Generally, this process suffers from low activity, low reaction selectivity, low stability of the catalysts and/or the use of noble-metal based catalysts. In this study, a highly efficient CuFe$_2$O$_4$-based photocatalyst is reported for the photocatalytic dehydrogenation of FAc under visible light at room temperature and under continuous gas flow. The effects of various factors such as composition of the catalysts and thermal pretreatment are investigated along a series of samples. The synthesis, dispersion, oxidation states, photo-electrochemical properties and performances of these materials were investigated in details. A synergetic effect, with relatively high dehydrogenation selectivity (77% with 6.6 mmol.g$^{-1}$ .h$^{-1}$ of H$_2$ production) is obtained on the copper-rich samples without any significant deactivation for two cycles of 20h/cycle. This study opens up a new route to design new Cu-based photocatalysts as cost-effective materials for visible-light driven photocatalytic dehydrogenation of FAc at room temperature.
Published: 2023
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8. Size-Dependent Photocatalytic Activity of Silver Nanoparticles Embedded in ZX-Bi Zeolite Supports

Author: Houeida Issa Hamoud, Fatima Douma, Mama Lafjah, Fatiha Djafri, Oleg Lebedev, Valentin Valtchev, Mohamad El-Roz, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université d'Oran 1 Ahmed Ben Bella [Oran], Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), 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), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: size effect, operando, plasmonic catalyst, General Materials Science, [CHIM.CATA]Chemical Sciences/Catalysis, Silver nanoparticles, photocatalysis
Abstract: International audience; In this study, the photocatalytic activity of highly dispersed silver embedded into ZX-Bi zeolite during methanol photooxidation under visible light and at room temperature is investigated. The size and dispersion of Agn δ+ sub-nanoclusters (< 1 nm) is studied by HR/TEM, DR-UV-Vis, in situ FTIR, etc. The catalytic tests were performed using the operando FTIR technique during methanol photooxidation as a model reaction. The results show that the as-prepared Ag/ZX-Bi was very low active, while the activated sample at 200 °C (Ag/ZX-Bi_200) exhibits the highest photocatalytic activity (49.60 mmol.g-1 .cm-2 after 12 h of reaction) during methanol photooxidation, more than 6 times higher than the TiO2-P25 used as reference. This activity originates from the migration and agglomeration of sub-nanosized Agn d+ clusters into Ag nanoparticles with a size of 6 nm. However, the catalyst experienced a partial desactivation when the particle size of sintered Ag NPs is below 20 nm. The activity and the deactivation of Ag/ZX-Bi will be discussed on the basis of operando FTIR results and HRTEM analysis at different stages of the reaction.
Published: 2022
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9. Ethane oxidative dehydrogenation with CO2 on thiogallates

Author: Vera Bikbaeva, Olivier Perez, Nikolay Nesterenko, Valentin Valtchev, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), and TotalEnergies OneTech Belgium
Subjects: Inorganic Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis
Abstract: International audience; The CO2-assisted oxidative dehydrogenation of ethane (ODH-CO2) attracts a lot of research interest since it combines greenhouse gas utilization with the production of valuable chemicals. The present study demonstrates the potential of the novel non-classic catalysts, alkali thiogallates, in this reaction. The contribution also reports a novel solvothermal synthesis method to prepare crystalline KGaS2 thiogallate materials. Despite the low surface area of the bulk KGaS2 system, the material shows substantial activity in CO2 to CO transformation with conversions in the range of 22-36% at 700-800 °C. The catalyst allows utilization of the co-produced hydrogen from ethane thermal cracking for CO2 hydrogenation without substantially impacting ethylene yield even at 800 o C at the conversion level of ethane close to 70%. The catalyst demonstrates stable performance with insignificant coke formation. The structure of the KGaS2 thiogallate material is fully conserved after the reaction. These results open a promising opportunity for the thiogallate materials as catalysts with moderate hydrogenation function, which are highly tolerant to the CO and highly reactive hydrocarbons environments.
Published: 2022
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10. Unlocking the Potential of Hidden Sites in Faujasite: New Insights in a Proton Transfer Mechanism

Author: Cassandre Kouvatas, Jean-Pierre Gilson, Hristiyan A. Aleksandrov, Nikolai Nesterenko, Louwanda Lakiss, Svetlana Mintova, Valentin Valtchev, N. Georgi vayssilov, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: Proton, 010405 organic chemistry, Industrial research, General Medicine, General Chemistry, Faujasite, engineering.material, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Computational chemistry, Transfer mechanism, Sodalite, engineering, [CHIM]Chemical Sciences, Zeolite, Derivative (chemistry)
Abstract: International audience; Zeolite Y and its ultra-stabilized hierarchical derivative (USY) are the most widely used zeolite-based heterogeneous catalysts in oil refining, petrochemisty, and other chemicals manufacturing. After almost 60 years of academic and industrial research, their resilience is unique as no other catalyst displaced them from key processes such as FCC and hydrocracking. The present study highlights the key difference leading to the exceptional catalytic performance of USY versus the parent zeolite Y in a multi-technique study combining advanced spectroscopies (IR and solid-state NMR) and molecular modeling. The set of results highlights a hitherto unreported proton transfer involving inaccessible active sites in sodalite cages that contributes to the exceptional catalytic performance of USY.
Published: 2021
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11. Direct synthesis of nanosized CHA zeolite free of organic template by a combination of cations as structure directing agents

Author: Maxime Debost, Edwin B. Clatworthy, Julien Grand, Nicolas Barrier, Nikolai Nesterenko, Jean-Pierre Gilson, Philippe Boullay, Svetlana Mintova, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), and TotalEnergies OneTech Belgium
Subjects: Mechanics of Materials, [CHIM]Chemical Sciences, General Materials Science, General Chemistry, Condensed Matter Physics
Abstract: International audience
Published: 2022
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12. Approche archéologique et environnementale des premiers peuplements alpins autour du col du Petit-Saint-Bernard (Savoie -Vallée d’Aoste) : un bilan d’étape

Author: Pierre-Jérôme Rey, Batigne-Vallet, C., Julien Collombet, Claire Delhon, Lucie Martin, Bernard Moulin, Jérôme Poulenard, Scocimaro, N., Dominique Sordoillet, Stéphanie Thielbaut, Jean-Michel Treffort, Sordoillet, Dominique, Tzortzis S., Delestre X., Environnements, Dynamiques et Territoires de la Montagne ( EDYTEM ), Université Savoie Mont Blanc ( USMB [Université de Savoie] [Université de Chambéry] ) -Centre National de la Recherche Scientifique ( CNRS ), Culture et Environnements, Préhistoire, Antiquité, Moyen-Age ( CEPAM ), Université Nice Sophia Antipolis ( UNS ), Université Côte d'Azur ( UCA ) -Université Côte d'Azur ( UCA ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire SUBATECH Nantes ( SUBATECH ), Mines Nantes ( Mines Nantes ) -Université de Nantes ( UN ) -Institut National de Physique Nucléaire et de Physique des Particules du CNRS ( IN2P3 ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire catalyse et spectrochimie ( LCS ), Université de Caen Normandie ( UNICAEN ), Normandie Université ( NU ) -Normandie Université ( NU ) -Ecole Nationale Supérieure d'Ingénieurs de Caen ( ENSICAEN ), Normandie Université ( NU ) -Centre National de la Recherche Scientifique ( CNRS ), Institut National de Recherches Archéologiques Préventives ( INRAP ), Institut national de recherches archéologiques préventives ( Inrap ), Laboratoire Chrono-environnement ( LCE ), Université Bourgogne Franche-Comté ( UBFC ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Franche-Comté ( UFC ), Archéologie, Terre, Histoire, Sociétés [Dijon] ( ARTeHiS ), Ministère de la Culture et de la Communication ( MCC ) -Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Environnements, Dynamiques et Territoires de la Montagne (EDYTEM), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Archéologie et Archéométrie (ArAr), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Université Lumière - Lyon 2 (UL2), Culture et Environnements, Préhistoire, Antiquité, Moyen-Age (CEPAM), Université Côte d'Azur (UCA)-Centre National de la Recherche Scientifique (CNRS)-Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA), Laboratoire SUBATECH Nantes (SUBATECH), Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Nantes (UN)-Mines Nantes (Mines Nantes), Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Institut national de recherches archéologiques préventives (Inrap), Laboratoire Chrono-environnement - CNRS - UBFC (UMR 6249) (LCE), Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC), Archéologie, Terre, Histoire, Sociétés [Dijon] (ARTeHiS), and Ministère de la Culture et de la Communication (MCC)-Université de Bourgogne (UB)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [SHS.ARCHEO] Humanities and Social Sciences/Archaeology and Prehistory, [SHS.ARCHEO]Humanities and Social Sciences/Archaeology and Prehistory, archeology, [ SHS.ARCHEO ] Humanities and Social Sciences/Archaeology and Prehistory, Alps, first settlements, ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2010

13. Effect of Sodium Concentration on the Synthesis of Faujasite by Two-step Synthesis Procedure

Author: Chunzheng Wang, Svetlana Mintova, Hailing Guo, Lei Zhao, Lijuan Wang, Ge Yang, Institut d'Électronique et des Technologies du numéRique (IETR), Université de Nantes (UN)-Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), China University of Petroleum, School of Mathematics and Statistics [Wuhan], Wuhan University [China], Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-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)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), and Nantes Université (NU)-Université de Rennes 1 (UR1)
Subjects: Materials science, synthesis, Sodium, chemistry.chemical_element, 02 engineering and technology, engineering.material, 010402 general chemistry, 01 natural sciences, law.invention, chemistry.chemical_compound, Aluminosilicate, law, morphology, [CHIM]Chemical Sciences, zeolite, alkali metal, Crystallization, Zeolite, General Chemistry, Faujasite, 021001 nanoscience & nanotechnology, Alkali metal, 0104 chemical sciences, Amorphous solid, chemistry, Sodium hydroxide, engineering, 0210 nano-technology, Nuclear chemistry
Abstract: International audience; The relationship between concentration of sodium cations and the properties of faujasite (FAU) zeolite using a two-step synthesis procedure including (1) formation of amorphous aluminosilicate precursors and separation of amorphous nanoparticles, and (2) transformation of these amorphous particles into zeolite crystals by treatment with alkali solutions (NaOH) were studied. Three representative samples including two nano-sized zeolites and one micron-sized zeolite were prepared using different concentration of sodium hydroxide. The crystallization process of these zeolites was studied in details by FTIR, NMR, XRD, SEM, TEM, N 2 adsorption. The results indicated that minor changes in the concertation of inorganic cations can significantly shorten the induction period and crystallization time and thus affect the morphology, size and chemical composition of the zeolite crystals.
Published: 2021
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14. Atomic-Insight into Zeolite Catalyst Forming—an Advanced NMR Study

Author: Cassandre Kouvatas, Suheil F. Abdo, Valentin Valtchev, Robert L. Bedard, Louwanda Lakiss, Svetlana Mintova, Jean-Pierre Gilson, Christian Fernandez, Jeffery C. Bricker, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: Materials science, 010405 organic chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Catalysis, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Energy, Chemical engineering, Physical and Theoretical Chemistry, Zeolite
Abstract: International audience; The main goal of this study is to understand, at the atomic level, the chemical interactions occurring between an active phase, a FAU zeolite in this case, and its binder during catalyst forming. This unit operation is a critical step in catalyst scale-up and commercialization but hasn't received the attention it deserves from academia. Herein, we present atomic-level insight in the solid-state chemistry taking place during the extrusion process by advanced NMR spectroscopy techniques (Indirect 27 Al{ 1 H}DNP MAS and 27 Al-{ 29 Si} J-HMQC). In particular, we: i) elucidate the chemical reactions taking place between atype Y FAU zeolite (Si/Al = 2.3) and abinder (pseudoboehmite), producing new active sites different than those present in either the zeolite or binder, ii) determine the location of these new active sites by a combination of DNP build-up time (TDNP)extracted from { 1 H}-27 Al saturation-recovery CP experiments and 2D heteronuclear 29 Si-27 Al NMR. This illustrates the power of advanced NMR techniques to elucidate the nature and location of newly created active sites during catalyst forming and provides insight into a key step to further fine-tune industrial catalysts.
Published: 2021
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15. Des nanoparticules métalliques supportées pour la dépollution de l’air

Author: Barrault, Joel, Valange, Sabine, Tatibouet, Jean-Michel, Thollon, Stephanie, Herlin-Boime, Nathalie, Sophie Giraud, Ruiz, Jean-Christophe, Fournel, Bruno, Bergaya, Badreddine, Joulin, Jean-Pierre, Delbianco, Nadine, Gabelica, Zelimir, Daturi, Marco, Laboratoire de catalyse en chimie organique (LACCO), Université de Poitiers-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Technologies des Surfaces (LTS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire Francis PERRIN (LFP - URA 2453), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Service des Photons, Atomes et Molécules (SPAM), Service des Recherches Métallurgiques Appliquées (SRMA), Département des Matériaux pour le Nucléaire (DMN), 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)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Laboratoire des Fluides Supercritiques et des Membranes (LFSM), Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Poitiers-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Lebe, Caroline, Catalyse en chimie organique ( LACCO ), Université de Poitiers-Centre National de la Recherche Scientifique ( CNRS ), Laboratoire Technologies des Surfaces ( LTS ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ), Laboratoire Francis PERRIN ( LFP - URA 2453 ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS ), Service des Photons, Atomes et Molécules ( SPAM ), Service des Recherches Métallurgiques Appliquées ( SRMA ), Département des Matériaux pour le Nucléaire ( DMN ), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ), Laboratoire des Fluides Supercritiques et des Membranes ( LFSM ), Laboratoire catalyse et spectrochimie ( LCS ), Université de Caen Normandie ( UNICAEN ), Normandie Université ( NU ) -Normandie Université ( NU ) -Ecole Nationale Supérieure d'Ingénieurs de Caen ( ENSICAEN ), and Normandie Université ( NU ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: Dispersed nanoparticles, laser pyrolysis, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, DLI-MOCVD, volatile organic compounds oxidation, supercritical CO2
Abstract: International audience; The main objectives of the "NACACOMO" Consortium ("Nanomaterials: Catalysts for the Conversion of organic Molecules. Uses in fine chemicals and environment protection") consisted in generating novel catalysts composed of nanoparticles of metals (Pt, Pd, Ag...) and/or oxides (TiO2...) stabilized and well distributed over the surface of a support (foams, ceramics), by monitoring both the particle size and the "coating" process itself, using new technologies: CVD, plasma-spray, laser pyrolysis, supercritical preparation, which were compared to conventional soft chemistry recipes. The most accurate characterization of particle morphology, local structure, texture, spatial arrangement but also of their reactivity, were achieved by privileging the utilization of various in situ methods. Details on formation mechanisms of a solid nanoparticle at the atomic level (nucleation, growth and particle (re)distribution over the support...) could be obtained in selected cases, with opportunities for scaling up and shaping. The (chemical) nature of the so-obtained nanomaterials was monitored for selected catalytic applications involving the development of environmental friendly processes, such as oxidation of VOC, with a priority for aromatics and chlorinated compounds.
Published: 2009

16. New Coupling Agent Structures for Preparing Filler-Polymer Hybrid Materials Under Soft Irradiation Conditions

Author: Houssein Nasrallah, Rita Zakhia Douaihy, Igor Telegeiev, Oleg I. Lebedev, Armand Fahs, Mohamad EL-Roz, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), Laboratoire Matériaux Polymères Interfaces Environnement Marin - EA 4323 (MAPIEM), and Université de Toulon (UTLN)
Subjects: Inorganic Chemistry, [CHIM.POLY]Chemical Sciences/Polymers, Polymers and Plastics, silica, polymer, hybrid materials, Organic Chemistry, Materials Chemistry, [CHIM]Chemical Sciences, [CHIM.MATE]Chemical Sciences/Material chemistry, Silane Based Photoinitiator (SPI)
Abstract: International audience; The bifunctional coupling agents have become unavoidable products for preparing hybrid materials with enhanced properties. They are at the origin of the homogeneous dispersion of the filler in the polymerizable matrix and the strong chemical interactions between the composites during the thermal reticulation and vulcanization processes. However, only few structures can play this role in a photo-curable matrix, which is widely applied today in various manufactures (3D printing, cosmetic, medicine, etc.). Developing new structures capable of working under accurate irradiation conditions can extend the use of coupling agents for preparing hybrid photo-curable materials for various applications (e.g. membrane, masks, 2D- and 3D- nano/micro-objects). Recently, a new SPI (SPI-1) was proposed by our group and has revealed a high efficiency for preparing filler-polymer hybrid material. Despite its efficiency, its activity is the highest under the UV-B irradiation but lower under UV-A and inactive under visible light. In this paper, new coupling agent structures (bifunctional Silane-based Photoinitiators; SPI) are synthesized and tested under various irradiation conditions extensively used in the photocuring fields (365, 385 and 405 nm). All the new structures demonstrate higher performance than the first SPI generation (SPI-1) under the diverse light sources. More particularly, SPI-4, 5, and 6 (triphenylamine-based SPI) demonstrate a remarkable activity for preparing filler-polymer hybrid materials under visible light irradiation (LED 405 nm). The efficiency of the new structures in the photopolymerization as well as in the grafting of the silica particles (used as filler model) is elucidated. Finally, the enhancement of the mechanical properties of the hybrid composite films and the possible use of the new approach in photolithography is also demonstrated.
Published: 2022
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17. Formulation of two monofunctionnal catalysts for CH4 upgrading

Author: Stanislav V. Konnov, Izabel C. Medeiros-Costa, Hugo Cruchade, Florent Dubray, Maxime Debost, Jean-Pierre Gilson, Valentin Valtchev, Jean-Pierre Dath, Nikolai Nesterenko, Svetlana Mintova, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Total Research and Technology Feluy ( [TRTF]), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), Centre National de la Recherche Scientifique (CNRS), Normandie Université (NU), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), and TotalEnergies OneTech Belgium
Subjects: Process Chemistry and Technology, [CHIM]Chemical Sciences, Catalysis
Abstract: International audience
Published: 2022
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18. Platelike MFI Crystals with Controlled Crystal Faces Aspect Ratio

Author: Valentin Valtchev, Cassandre Kouvatas, Naijia Guan, Weijiong Dai, Wenshu Tai, Guangjun Wu, Landong Li, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: Morphology, Zeolite, Ultra-thin crystals, Chemistry, Diffusion, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Aspect ratio (image), Catalysis, 0104 chemical sciences, law.invention, Crystal, Colloid and Surface Chemistry, Chemical engineering, law, [CHIM]Chemical Sciences, Molecule, Nanometre, Crystallization
Abstract: International audience; Zeolite crystals offering a short diffusion pathway through the pore network are highly desired for a number of catalytic and molecule separation applications. Herein, we develop a simple synthetic strategy toward reducing the thickness along b-axis of MFI-type crystals, thus providing a short diffusion path along the straight channel. Our approach combines preliminary aging and a fluoride-assisted low-temperature crystallization. The synthesized MFI crystals are in the micron-size range along a-and c-axis, while the thickness along the b-axis is a few tens of nanometers. The synthesis parameters controlling the formation of plate-like zeolite are studied, and the factors controlling the zeolite growth identified. The synthesis strategy works equally well with all-silica MFI (silicalite-1) and its Al-and Ga-containing derivatives. The catalytic activity of plate-like ZSM-5 in the methanol-to-hydrocarbons (MTH) reaction is compared with a commercial nano-sized ZSM-5 sample, as the plate-like ZSM-5 exhibits a substantially extended lifetime. The synthesis of plate-like MFI crystals is successfully scaled up to a kilogram scale.
Published: 2021
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19. Cu- and Fe-speciation in a composite zeolite catalyst for selective catalytic reduction of NOx: insights from operando XAS

Author: Marco Daturi, Valentin Valtchev, Houeida Issa Hamoud, Andrea Martini, Søren Birk Rasmussen, Carlo Lamberti, Kirill A. Lomachenko, Silvia Bordiga, I. A. Pankin, Philippe Bazin, Dipartimento di Chimica [Torino], Università degli studi di Torino (UNITO), Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: X-ray absorption spectroscopy, Materials science, Absorption spectroscopy, Extended X-ray absorption fine structure, 010405 organic chemistry, Selective catalytic reduction, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Catalysis, XANES, 0104 chemical sciences, Chemical engineering, Zeolite, NOx
Abstract: Cu-SAPO-34 (Cu-CZC) and Fe-mordenite (Fe-MOR) and their mechanical mixture (50 : 50) have been exhaustively investigated by means of operando X-ray absorption spectroscopy under NH3-SCR conditions. Fe K-edge XANES and EXAFS analysis revealed similar Fe-speciation in both the pure Fe-MOR catalyst and the mechanical mixture after high-temperature pretreatment and under reaction conditions. In contrast, analysis of the Cu K-edge dataset unveiled different trends in temperature-driven Cu-speciation in the pure Cu-CZC and mechanical mixture under standard NH3-SCR conditions. This difference is more evident in a low-temperature range. The presence of the Fe-MOR component in the mixed catalyst can result in the increase of NH3 and NO concentration in the proximity of Cu-sites at a low temperature regime, which facilitates temperature-driven migration of NH3-solvated mobile di-amino complexes from Cu-CZC to the MOR framework. This decreases the density of mobile CuI complexes in the entire system and results in the higher reducibility of Cu in the mixed catalyst. The obtained results help in understanding the precise speciation of the active sites in such composite catalysts and thus provide future guidance on design of such systems.
Published: 2021
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20. Crystallization pathway from a highly viscous colloidal suspension to ultra-small FAU zeolite nanocrystals

Author: Jeffery C. Bricker, Suheil F. Abdo, Louwanda Lakiss, Shrikant M. Kunjir, Valentin Valtchev, Svetlana Mintova, Christian Fernandez, Robert L. Bedard, Richard Retoux, Aurélie Vicente, Hussein Awala, Jean-Pierre Gilson, Hussein Seblani, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC), Honeywell, Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Renewable Energy, Sustainability and the Environment, Nanoparticle, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Amorphous solid, Suspension (chemistry), law.invention, Colloid, Chemical engineering, law, [CHIM]Chemical Sciences, Hydrothermal synthesis, General Materials Science, Particle size, Crystallization, 0210 nano-technology, Zeolite
Abstract: International audience; The crystallization kinetics of template free ultra-small FAU-type zeolite (X) in highly alkaline viscous precursor suspensions is investigated. We focus on understanding the crystallization pathway from a viscous amorphous precursor suspension into nanosized FAU crystals with high phase purity and yield. The crystallization develops in a four-step process: (1) preparation of a clear and stable precursor suspension by a controlled mixing of silica and alumina colloidal suspensions at low temperature (4 °C), (2) aging the colloidal suspension at room temperature, (3) partial evaporation of water of the colloidal suspension to produce a highly viscous suspension with an amorphous nanoparticles with a monomodal particle size distribution, (4) hydrothermal treatment at low temperature (50 °C) to transform the amorphous nanoparticles into FAU type nanocrystals with the same particle size while preventing agglomeration and sedimentation. The properties (size and morphology) of the amorphous particles depend on the mixing procedure (temperature and speed of mixing) and alkalinity of the colloidal suspension. The high alkalinity of the suspension leads to the formation of ultra-small discrete nanoparticles with a monomodal particle size distribution. During the aging step (2), secondary building units characteristic of the FAU framework structure are detected (Raman and IR spectroscopy) in the amorphous aluminosilicate particles. During the evaporation of water of the colloidal suspension (3), prior to hydrothermal synthesis, double-six membered rings (D6R), the secondary building units of the FAU structure were detected by insitu 29 Si NMR spectroscopy. Formation of the very first micropores in the nanosized particles was further confirmed by HP 129 Xe NMR spectroscopic measurements.
Published: 2021
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21. Synthesis of Discrete CHA Zeolite Nanocrystals without Organic Templates for Selective CO 2 Capture

Author: Maxime Debost, Fabien Laine, Paul Benjamin Klar, Philippe Boullay, Julien Grand, Svetlana Mintova, Nicolas Barrier, Nikolai Nesterenko, Lukáš Palatinus, Petr Brázda, Edwin B. Clatworthy, Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), Laboratoire catalyse et spectrochimie (LCS), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institute of Physics of the Czech Academy of Sciences (FZU / CAS), Czech Academy of Sciences [Prague] (CAS), Total Research and Technology Feluy ( [TRTF]), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: Chabazite, Materials science, education, 02 engineering and technology, Template-free synthesis, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, Colloid, Adsorption, Aluminosilicate, [CHIM]Chemical Sciences, Molecule, Zeolite, ComputingMilieux_MISCELLANEOUS, Precession-assisted 3D ED, 010405 organic chemistry, Sorption, General Chemistry, General Medicine, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemical engineering, Nanocrystal, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], In situ PXRD, Nanozeolites, CO2 adsorption, 0210 nano-technology
Abstract: International audience; Small-pore zeolites such as chabazite (CHA) are excellent candidates for the selective separation of CO2; however, the current synthesis involves several steps and the use of organic structure-directing agent (OSDA), increasing their cost and energy requirements. We report the synthesis of small-pore zeolite crystals (aluminosilicate) with CHA-type framework structure by direct synthesis in a colloidal suspension containing a mixture of inorganic cations only (Na+, K+, and Cs+). The location of CO2 molecules in the host structure was revealed by 3D electron diffraction (3D ED). The high sorption capacity for CO2 (3.8 mmol g−1 at 121 kPa), structural stability and regenerability of the discreate CHA zeolite nanocrystals is maintained for 10 consecutive cycles without any visible degradation. The CHA zeolite (Si:Al=2) reaches an almost perfect CO2 storage capacity (8 CO2 per unit cell) and high selectivity (no CH4 was adsorbed).
Published: 2020
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22. Emphasis on the Properties of Metal‐Containing Zeolites Operating Outside the Comfort Zone of Current Heterogeneous Catalytic Reactions

Author: Nikolai Nesterenko, Svetlana Mintova, Florent Dubray, Jean-Pierre Gilson, Stanislav V. Konnov, Edwin B. Clatworthy, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: Materials science, Biomass, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, Metal, Zeolite, Reaction conditions, Alkane, chemistry.chemical_classification, 010405 organic chemistry, business.industry, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Medicine, 021001 nanoscience & nanotechnology, Renewable energy, 0104 chemical sciences, chemistry, Chemical engineering, visual_art, visual_art.visual_art_medium, Current (fluid), business, 0210 nano-technology
Abstract: International audience; The development of catalysts that can operate under exceptionally harsh and unconventional conditions is of critical importance for the transition of the energy and chemicals industries to low-emission and renewable chemical feedstocks. In this review we will highlight materials and more specifically metal-containing zeolite catalysts that have been tested under harsh reaction conditions such as high temperature light alkane conversion and biomass valorization. Particular attention will be given to studies that explore the stability and recyclability of metal-containing zeolite catalysts operating in continuous modes. Metal-containing zeolites are considered as an important class of catalysts operating outside the comfort zone of current heterogeneous catalytic reactions in both gas and liquid phase reactions. The relationship between the properties of the metalcontaining zeolite and catalytic performance will be explored.
Published: 2020
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23. Diffusion and catalyst efficiency in hierarchical zeolite catalysts

Author: Xionghou Gao, Svetlana Mintova, Zifeng Yan, Peng Peng, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: Materials science, AcademicSubjects/SCI00010, pore connectivity, Diffusion, Industrial catalysts, Review, 02 engineering and technology, 010402 general chemistry, Fluid catalytic cracking, Interconnectivity, MATERIALS SCIENCE, 01 natural sciences, Catalysis, [CHIM]Chemical Sciences, Zeolite, ComputingMilieux_MISCELLANEOUS, Multidisciplinary, Chemical reaction engineering, diffusion, advanced characterization, 021001 nanoscience & nanotechnology, industrial catalyst, 0104 chemical sciences, Special Topic: Hierarchically Porous Materials, Chemical engineering, hierarchical zeolite, effectiveness factor, AcademicSubjects/MED00010, 0210 nano-technology, Mesoporous material
Abstract: The preparation of hierarchical zeolites with reduced diffusion limitation and enhanced catalyst efficiency has become a vital focus in the field of zeolites and porous materials chemistry within the past decades. This review will focus on the diffusion and catalyst efficiency of hierarchical zeolites and industrial catalysts. The benefits of diffusion and catalyst efficiency at two levels of hierarchies (zeolitic component level and industrial catalyst level) from a chemical reaction engineering point of view will be analysed. At zeolitic component level, three types of mesopores based on the strategies applied toward enhancing the catalyst effectiveness factor are presented: (i) ‘functional mesopores’ (raising effective diffusivity); (ii) ‘auxiliary mesopores’ (decreasing diffusion length); and (iii) ‘integrated mesopores’ (a combination thereof). At industrial catalyst level, location and interconnectivity among the constitutive components are revealed. The hierarchical pore interconnectivity in multi-component zeolite based industrial catalysts is exemplified by fluid catalytic cracking and bi-functional hydroisomerization catalysts. The rational design of industrial zeolite catalysts at both hierarchical zeolitic component and catalyst body levels can be fully comprehended using the advanced in situ and/or operando spectroscopic, microscopic and diffraction techniques.
Published: 2020
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24. Novel Strategy for the Synthesis of Ultra‐Stable Single‐Site Mo‐ZSM‐5 Zeolite Nanocrystals

Author: Svetlana Mintova, Jean-Pierre Dath, Delphine Minoux, Valentin Valtchev, Cassandre Kouvatas, Siddardha Koneti, Edwin B. Clatworthy, Cindy Aquino, Florent Dubray, Jean-Pierre Gilson, Nikolai Nesterenko, Simona Moldovan, Stanislav V. Konnov, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Groupe de physique des matériaux (GPM), Centre National de la Recherche Scientifique (CNRS)-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)-Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Total Research and Technology Feluy ( [TRTF]), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-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)-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)-Université de Caen Normandie (UNICAEN), 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), and ANR-11-EQPX-0020,GENESIS,Groupe d'Etudes et de Nanoanalyses des Effets d'IrradiationS(2011)
Subjects: Materials science, Hydrogen, 010405 organic chemistry, chemistry.chemical_element, General Medicine, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, Hydrothermal circulation, Methane, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Chemical engineering, Nanocrystal, Thermal stability, Zeolite, Hydrogen production
Abstract: International audience; The current energy transition presents many technological challenges, such as the development of highly stable catalysts. Herein, we report a novel "top-down" synthesis approach for preparation of a single-site Mo-containing nanosized ZSM-5 zeolite possessing atomically dispersed framework-molybdenum homogenously distributed through the zeolite crystals. The introduction of Mo heals most of the native point defects in the zeolite structure resulting in an extremely stable material. The important features of this single-site Mo-containing ZSM-5 zeolite are provided by an in-depth spectroscopic and microscopic analysis. The material demonstrates superior thermal (up to 1000 °C), hydrothermal (steaming), and catalytic (converting methane to hydrogen and higher hydrocarbons) stability, maintaining the atomically disperse Mo, structural integrity of the zeolite, and preventing the formation of silanols.
Published: 2020
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25. Busting the efficiency of SAPO-34 catalysts for the methanol-to-olefin conversion by post-synthesis methods

Author: Xiaoxin Chen, Guoju Yang, Valentin Valtchev, Ji Han, Yujun Huang, Jilin University (JLU), Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: Mass transport, Environmental Engineering, Materials science, Post-synthesis treatment, General Chemical Engineering, Industrial production, 02 engineering and technology, Post synthesis, Biochemistry, Hierarchical, Catalysis, chemistry.chemical_compound, 020401 chemical engineering, SAPO-34, 0204 chemical engineering, Zeolite, Olefin fiber, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Microporous material, 021001 nanoscience & nanotechnology, chemistry, Chemical engineering, Zeolites, Methanol, MTO, 0210 nano-technology
Abstract: International audience; As an effective non-petroleum based process for producing light olefins, the methanol-to-olefin (MTO) route has become an indispensable alternative to the industrial production of light olefins. The silicoaluminophosphate SAPO-34 zeolite (CHA-type structure) has proven to be an efficient industrial catalyst for the production of ethylene and propylene by the MTO reaction. However, the inherent structure and related diffusion limitations of SAPO-34 limit the mass transport and thus cause rapid deactivation of the catalyst. Fabrication of hierarchical SAPO-34 zeolite is one of the most effective strategies to address the intrinsic diffusion limitation. As simple, inexpensive, and efficient approach, the post-synthetic route has attracted considerable attention and widely used to introduce secondary meso-/macropores into the microporous SAPO-34 material. Significant effort has been dedicated to the development of post-synthesis strategies to prepare hierarchical 2 SAPO-34 zeolite, thereby enhancing its catalytic performance in the MTO process. This mini-review addresses the post-synthesis preparation of hierarchical SAPO-34 catalysts and their MTO performance. Furthermore, some current problems and prospects of the post-synthesis route to hierarchical SAPO-34 catalysts are also revised. We expect this mini-review to inspire the more efficient preparation of hierarchical SAPO-34 catalysts for the MTO process.
Published: 2020
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26. Probing the acid sites of zeolites with pyridine: Quantitative AGIR measurements of the molar absorption coefficients

Author: Cátia Freitas, Vladimir L. Zholobenko, Frédéric Thibault-Starzyk, Philippe Bazin, Arnaud Travert, Martin Jendrlin, Keele University [Keele], Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: pyridine, acid sites, Analytical chemistry, zeolites, Q1, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Adsorption, Pyridine, [CHIM]Chemical Sciences, QD, Sample preparation, Lewis acids and bases, Physical and Theoretical Chemistry, Fourier transform infrared spectroscopy, Zeolite, molar absorption coefficients, 010405 organic chemistry, Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Thermogravimetry, FTIR, Absorption (chemistry)
Abstract: International audience; This study presents a detailed methodology, which combines high-precision thermogravimetry and FTIR spectroscopy, aiming to establish the most accurate and reliable means of measuring the molar absorption coefficients of adsorbed species. As the integrated molar absorption coefficients of Py complexes with Brønsted and Lewis acid sites, ɛ(Py-B) and ɛ(Py-L), are determined and the validity of the Beer-Lambert-Bouguer law for IR characterisation of solid acids is demonstrated, this work is setting a benchmark for the quantitative acidity measurements in zeolites and related materials. The following values of ɛ(Py-B) have been obtained at 150°C (band at ~1545 cm-1): 1.09±0.08 cm µmol-1 for ZSM-5; 1.12±0.16 cm µmol-1 for BEA; 1.29±0.04 cm µmol-1 for MOR and 1.54±0.15 cm µmol-1 for FAU. The value of ɛ(Py-L) (band at ~1455 cm-1 , which refers to different cations) measured at the same temperature is 1.71±0.1 cm µmol-1. Values of ɛ(Py-B) depend on the zeolite structure, in contrast to that for ɛ(Py-L). Clear correlations are presented between the temperature of the FTIR measurements and ɛ values for Py complexes and other species, which decrease by ~10% as the temperature increases by 100oC. In addition, the effects of key experimental procedures, instrumentation design and sample preparation are established and quantified.
Published: 2020
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27. Internalization study of nanosized zeolite crystals in human glioblastoma cells

Author: Charly Helaine, Hayriye Özçelik, Sarah Komaty, Abdallah Amedlous, Sajjad Ghojavand, Didier Goux, Richard Retoux, Svetlana Mintova, Samuel Valable, Imagerie et Stratégies Thérapeutiques pour les Cancers et Tissus cérébraux (ISTCT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), 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), Laboratoire catalyse et spectrochimie (LCS), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Interactions Cellules Organismes Environnement (ICORE), Normandie Université (NU)-Normandie Université (NU)-CHU Caen, Normandie Université (NU)-Tumorothèque de Caen Basse-Normandie (TCBN)-Tumorothèque de Caen Basse-Normandie (TCBN), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), and INCA PLBIO 11699
Subjects: Colloidal suspension, Cell uptake, Nanosized zeolite, Cytotoxicity, [SDV]Life Sciences [q-bio], Surfaces and Interfaces, General Medicine, Faujasite, Oxygen, Colloid and Surface Chemistry, Zeolites, [CHIM]Chemical Sciences, Humans, Tissue Distribution, Physical and Theoretical Chemistry, Glioblastoma, Hypoxia, Biotechnology
Abstract: CERVOXY; International audience; While the use of nanozeolites for cancer treatment holds a great promise, it also requires a better understanding of the interaction between the zeolite nanoparticles and cancer cells and notably their internalization and biodistribution. It is particularly important in situation of hypoxia, a very common situations in aggressive cancers, which may change the energetic processes required for cellular uptake. Herein, we studied, in vitro, the kinetics of the internalization process and the intracellular localization of nanosized zeolite X (FAU-X) into glioblastoma cells. In normoxic conditions, scanning electron microscopy (SEM) showed a rapid cell membrane adhesion of zeolite nanoparticles (< 5 min following application in the cell medium), occurring before an energy-dependent uptake which appeared between 1 h and 4 h. Additionally, transmission electron microscopy (TEM) and flow cytometry analyzes, confirmed that the zeolite nanoparticles accumulate over time into the cytoplasm and were mostly located into vesicles visible at least up to 6 days. Interestingly, the uptake of zeolite nanoparticles was found to be dependent on oxygen concentration, i.e. an increase in internalization in severe hypoxia (0.2 % of O2) was observed. No toxicity of zeolite FAU-X nanoparticles was detected after 24 h and 72 h. The results clearly showed that the nanosized zeolites crystals were rapidly internalized via energy-requiring mechanism by cancer cells and even more in the hypoxic conditions. Once the zeolite nanoparticles were internalized into cells, they appeared to be safe and stable and therefore, they are envisioned to be used as carrier of various compounds to target cancer cells.
Published: 2022
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28. Access to sodalite cages in ion-exchanged nanosized FAU zeolites probed by hyperpolarized 129Xe NMR and DFT calculations

Author: Eddy Dib, Jérôme Rey, Aurelie Vicente, Shrikant Kunjir, Hussein Awala, Sarah Komaty, Ayoub Daouli, Tomáš Bučko, Hussein El Siblani, Robert Bedard, Jeffery Bricker, Jean-Pierre Gilson, Michael Badawi, Svetlana Mintova, 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), Institut Paoli-Calmettes, Fédération nationale des Centres de lutte contre le Cancer (FNCLCC), Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), 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), Laboratoire de Physique et Chimie Théoriques (LPCT), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Comenius University in Bratislava, Slovak Academy of Science [Bratislava] (SAS), and Honeywell
Subjects: Mechanics of Materials, [CHIM]Chemical Sciences, General Materials Science, General Chemistry, Condensed Matter Physics
Abstract: International audience
Published: 2022
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29. Kinetics and oxygen dependence of uptake of nanozeolites by human glioblastoma cells

Author: Hélaine, C, Özçelik, Hayriye, Komaty, S., Amedlous, A., Ghojavand, Sajjad, Goux, Didier, Retoux, Richard, Mintova, Svetlana, Samuel, Valable, Imagerie et Stratégies Thérapeutiques pour les Cancers et Tissus cérébraux (ISTCT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire catalyse et spectrochimie (LCS), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [SDV]Life Sciences [q-bio]
Abstract: CERVOXY; National audience
Published: 2022

30. Investigation of interactions between organophosphorus compounds and TiO2 modified microcantilevers for molecule detection in air

Author: Urelle Biapo, Valérie Keller, Philippe Bazin, Thomas Cottineau, Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-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)-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), Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Cottineau, Thomas
Subjects: Chemistry (miscellaneous), [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, General Materials Science
Abstract: International audience; In order to develop a detector working in the gas phase for organophosphorus molecules, resonant microcantilever surfaces were chemically modified with pristine and functionalized TiO 2 nanorods. By using a solvothermal synthesis method a homogeneous film, composed of nanorods with square facets, covering completely the surface of the levers was obtained. The synthesized rods mainly exhibit [110] oriented crystals and this facet has especially demonstrated a high loading ability for grafted sensing molecules. Experimental results showed that the sensing response is three times higher when the TiO 2 sensor is functionalized with amine terminated molecules while no significant response is observed for bare cantilevers exposed to a DMMP simulant. The in situ IR analysis highlighted the formation of hydrogen bonds between the characteristic groups of DMMP and the TiO 2 surface at room temperature. The strength of this bond depends on the chemical groups present at the oxide surface. Molecules containing hydroxyl or amino functions form stronger hydrogen interactions with the OP simulant compared to the fluorine group. The kinetics of adsorption are characterized by a fast initial reaction followed by gradual slowing to a steady-state for all the samples.
Published: 2022
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31. Infrared Spectroscopic Evidence of WS2 Morphology Change With Citric Acid Addition and Sulfidation Temperature

Author: Luz A. Zavala-Sanchez, Françoise Maugé, Xavier Portier, Laetitia Oliviero, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), 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), 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), and METSA (Ref #2020B161)
Subjects: Technology, [PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics], Chemical technology, infrared (IR), WS2, TP1-1185, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, citric acid, [SPI.MAT]Engineering Sciences [physics]/Materials, [PHYS.PHYS.PHYS-COMP-PH]Physics [physics]/Physics [physics]/Computational Physics [physics.comp-ph], [SPI.ELEC]Engineering Sciences [physics]/Electromagnetism, [SPI.OPTI]Engineering Sciences [physics]/Optics / Photonic, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], CO adsorption, hydrotreating catalysts, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, hydrodesulfurization
Abstract: MS2 morphology is strongly influenced by several parameters including the addition of a chelating agent and sulfidation temperature. In this work, we report the use of citric acid as chelating agent in order to prepare a series of WS2/Al2O3 catalysts that were submitted to sulfidation at several temperatures. The effect of these two parameters in the morphology of the slabs was explored by means of CO adsorption at low temperature followed by IR spectroscopy (IR/CO) and later confirmed by High-Resolution Scanning Transmission Electron Microscopy coupled with High Angular Annular Dark Field detector (HR STEM - HAADF). This allowed to depict the morphology of WS2 slabs by means of calculating the M-edge/S-edge site ratio. The use of citric acid in the preparation stage favors the increase of S-edge site concentration whereas it keeps that of M-edge sites: according to IR/CO, with an increasing amount of citric acid, the WS2 morphology progressively changes from a slightly truncated triangle exhibiting predominantly M edges to a hexagon with both M edge and S edge. In addition, HR STEM-HAADF demonstrated that the addition of citric acid in the impregnation step of W catalysts considerably reduces the size of WS2 nanoparticles increasing their dispersion degree. The morphology of the WS2 plates on the activated WS2/Al2O3 catalyst with a typical sulfidation temperature range (573–673 K) was detected to be a truncated triangle exposing both the M-edge and the S-edge. Furthermore, the IR/CO results indicate that the degree of truncation (ratio of S-edge/M-edge) of WS2 slabs gradually rises with the increasing sulfidation temperature. However, the most determining factor for a modification of the morphology of the slabs turns out to be the presence of citric acid as a chelating agent and not the sulfidation temperature. This change in morphology (i.e., change of S-edge/M-edge ratio) is a key factor for catalytic performance, since the M-edge and the S-edge show different reactivity in hydrodesulfurization (HDS) reactions. Notably, it was also found that the addition of citric acid not only improves the catalytic activity but also the stability of the catalysts, giving the best performance in concentrations higher than (CA/W = 1).
Published: 2022
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32. Toward Economical Seawater-Based Methane Hydrate Formation at Ambient Temperature: A Combined Experimental and Computational Study

Author: Ahmed Omran, Nikolay Nesterenko, Arnold A. Paecklar, Nicolas Barrier, Valentin Valtchev, École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), TotalEnergies OneTech Belgium, Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.GENI]Chemical Sciences/Chemical engineering, Renewable Energy, Sustainability and the Environment, General Chemical Engineering, Environmental Chemistry, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, General Chemistry, [SPI.MAT]Engineering Sciences [physics]/Materials
Abstract: International audience; Clathrate hydrates are emerging as a novel storage medium for safe and compact methane storage. However, their industrial-scale applicability is hindered by sluggish formation kinetics and intense energy cooling requirements. The present study is the first report on binary methane-tetrahydrofuran (THF) formation using seawater and an unstirred reactor at ambient temperature (298.2 K) that would improve the process economics. Acidic zeolites with different Si/Al ratios (USY-40 and USY-10) as well as aliphatic and aromatic amino acids (L-valine and L-tryptophane) are employed as environmentally benign kinetic hydrate promoters. The experimental study is combined with DFT calculations to shed light on the role of kinetic promoters in hydrates formation. The set of experimental data revealed that hydrophobic zeolites with a higher Si/Al ratio performed better than the more hydrophilic ones. Moreover, the aliphatic amino acid L-valine showed better kinetic promotion performance for hydrate formation in natural and artificial seawater than the aromatic amino acid L-tryptophan. The optimization of the experimental conditions allowed a controlled hydrate growth boosting the gas uptake to 40 mmol gas/mol water, which is the highest reported under mild conditions using seawater. In addition, the induction time is reduced to less than 10 minutes, and a methane recovery of 97% is reached without any foaming signs. Thus, this study demonstrates the possibility of controlling the stochastic nature of nucleation and hydrate growth by proper manipulation of the reaction system. Our results provide a better understanding of hydrate nucleation enhancement under realistic conditions and open the door for a possible application of these environmentally benign KHPs for synthetic natural gas (SGH) on a continuous process and industrial scale.
Published: 2022
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33. Synthesis of core-shell magnetic nanoparticles containing ultra-small domains of silicalite-1

Author: Diógenes Honorato Piva, Roger Honorato Piva, Sajjad Ghojavand, Alain Pautrat, Maxime Debost, Ernesto A. Urquieta‐González, Svetlana Mintova, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Mechanics of Materials, Mechanical Engineering, [CHIM]Chemical Sciences
Abstract: International audience
Published: 2022
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34. A comparison of layered materials used as catalysts for diols conversion

Author: Bekkali, Hamza, Boullay, Philippe, Clet, Guillaume, Clet, Guillaume, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-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), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, [CHIM.ANAL] Chemical Sciences/Analytical chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract: International audience
Published: 2022

35. Silicalite-1 formation in acidic medium: synthesis conditions and physicochemical properties

Author: Qisong Yi, Xiaobo Yang, Haonuan Zhao, Hailing Guo, Guangying Fu, Valentin Valtchev, Eddy Dib, Juan Wang, Qiaolin Lang, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), and Valtchev, Valentin
Subjects: Colloidal silica, Kinetics, crystal size control, Crystal growth, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Catalysis, Crystal, Crystallinity, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, General Materials Science, Thermal stability, Zeolite, Chemistry, General Chemistry, seeding with zeolitic embyos, structure integrity and thermal stability, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Zeolite crystallization in acidic medium, Chemical engineering, Mechanics of Materials, 0210 nano-technology, defect-free silicalite-1
Abstract: International audience; Zeolites are the catalytic materials that are widly applied in the processing of conventional and renewable fuels and chemicals. The present study provides a comprehensive analysis of the factors controlling the acidic medium synthesis of high silica silicalite-1 zeolite. The effect of various silica sources (TEOS, fumed and colloidal silica) and alkali metal cations (Na and K) on the silicalite-1 formation is studied. The efficiency of different types of seeds (micron-sized, nanosized, and silicalite-1 amorphous colloidal precursor) on the silicalite-1 crystal growth kinetics and crystal size formed under acidic conditions is also investigated. Further, the zeolite crystallization kinetics under acidic, neutral, and basic conditions is compared. The obtained highly crystalline samples are used to compare the physicochemical properties of zeolites synthesized in acidic, neutral, and basic medium. Thus, the crystallinity, thermal stability, and local order in silicalite-1 samples synthesized in the (2-12) pH range are evaluated.
Published: 2022

36. Highly efficient CO2 reduction under visible-light on non-covalent Ru⋯Re assembled photocatalyst: Evidence on the electron transfer mechanism

Author: Pengbo Lyu, Guillaume Maurin, Houssein Nasrallah, Mohamad El-Roz, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-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), Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: 010405 organic chemistry, Chemistry, Hydrogen bond, Stacking, Quantum yield, electron transfer, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Artificial photosynthesis, Supramolecular assembly, Electron transfer, CO2 photoreduction, Photocatalysis, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, supramolecular assembly, Bimetallic strip, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Herein, two complexes: Pyrene modified photosensitizer (RuPy) and catalyst (ReCOPy) were synthetized and combined to form a novel bimetallic supramolecular assembly RuPy•••ReCOPy via a combination of π-π stacking and hydrogen bond interactions. This supramolecular assembly was further characterized by electrochemical and spectroscopic techniques in order to determine its redox and photochemical properties. This novel RuPy•••ReCOPy supramolecular assembly was demonstrated to display a high level of performance for the photocatalytic conversion of CO2 conversion into CO with turn over frequency and CO quantum yield much higher (TOF: 18 h-1 , ΦCO: 0.77) than the value obtained for the benchmark system Ru(bpy)3Cl2 (Ru) with Re(bpy)(CO)3Cl (ReCO) (5.3 h-1 , ΦCO : 0.38). Time resolved spectroscopy and Density Functional Theory calculations revealed that an electron transfer mechanism is at the origin of the highly photocatalytic performance of RuPy•••ReCOPy.
Published: 2021
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37. Defect Sites in Zeolites: Origin and Healing

Author: Palčić, Ana, Moldovan, Simona, Siblani, Hussein, Vicente, Aurelie, El Siblani, Hussein, Valtchev, Valentin, Ruđer Bošković Institute, 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), Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), 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), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Valtchev, Valentin
Subjects: silanols, 010405 organic chemistry, General Chemical Engineering, Science, General Engineering, General Physics and Astronomy, Medicine (miscellaneous), zeolites, 010402 general chemistry, 01 natural sciences, Biochemistry, Genetics and Molecular Biology (miscellaneous), 0104 chemical sciences, postsynthesis treatment, Chemistry, post-synthesis treatment, [CHIM] Chemical Sciences, defect sites, Al/Si incorporation, [CHIM]Chemical Sciences, General Materials Science, ComputingMilieux_MISCELLANEOUS
Abstract: This paper deals with the synthesis conditions–defect formation relationship in zeolites. Silicalite-1 (MFI-type) is used as a model material. Samples synthesized from a system with high basicity (at 100 °C), a system with moderate basicity (at 150 °C), and a fluoride- containing system in neutral medium (at 170 °C) were compared. Well-crystallized materials with sizes ca. 0.1, 1-10, and 30-40 µm were obtained. The samples are analyzed by complementary methods providing information on the short- and long-range order in the zeolite framework. A strong correlation between the number of point defects in the zeolite framework and preparation conditions is established. Silicalite-1 synthesized under mild synthesis conditions from a highly basic system exhibits a larger number of framework defects and thus low hydrophobicity. Further, the calcined samples were subjected to aluminum and silicon incorporation by post- synthesis treatment. The Al/Si incorporation in the zeolite framework and its impact on the physicochemical properties is studied by XRD, TEM/SEM, solid-state NMR, FTIR, and thermogravimetric analyses. The defects healing as a function of the number of point defects in the initial material and zeolite crystal size is evaluated. The results of this study will serve for fine-tuning zeolite properties by in situ and post-synthesis methods.
Published: 2021
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38. Preparation of HKUST-1/PEI mixed-matrix membranes: adsorption-diffusion coupling control of small gas molecules

Author: Rémy Guillet-Nicolas, Xianglong Meng, Svetlana Mintova, Guodong Kong, Yanjiao Wang, Hailing Guo, Zixi Kang, Ge Yang, China University of Petroleum, Quantachrome Instruments, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: capping agent, Materials science, Filtration and Separation, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, mixed-matrix membrane, chemistry.chemical_compound, Adsorption, [CHIM]Chemical Sciences, General Materials Science, Physical and Theoretical Chemistry, interfacial defects, gas separation, chemistry.chemical_classification, Sodium formate, Polymer, HKUST-1 nanocrystals, 021001 nanoscience & nanotechnology, Polyetherimide, 0104 chemical sciences, Membrane, chemistry, Chemical engineering, Nanocrystal, 0210 nano-technology, Selectivity, Syngas
Abstract: International audience; HKUST-1 nanocrystals (50-80 nm) were homogeneously dispersed in a polyetherimide (PEI) polymer matrix. The use of a capping agent (sodium formate) 2 prevented the agglomeration of HKUST-1 nanocrystals in the casting solution. The highly dispersed HKUST-1 nanocrystals were found to strengthen the interactions with the PEI and minimize the interfacial holes by providing more accessible Cu unsaturated metal sites for the C=O bonds on the five-membered rings of the PEI matrix. The PEI membrane loaded with 30 wt. % HKUST-1 nanocrystals (30-N-HKUST-1/PEI) showed a high H 2 permeability (193.3 Barrer at 25 °C under 1.5 bar) and good ideal H 2 /CH 4 and H 2 /CO 2 selectivity factor of 101.7 and 20.6 in a single gas test, respectively. In the gas mixture test, it also showed a good separation performance, i.e., a H 2 /CH 4 and H 2 /CO 2 selectivity factor of 82.4 and 16.5 was measured, respectively. The 30-N-HKUST/PEI membrane was tested in a gas mixture at different temperatures (25-100 °C), different pressures (0-3 bar) and various time (5-72 h) to study the performance in more realistic conditions thus to be further considered in the separation of syngas.
Published: 2021
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39. Synthesis and catalytic application of nanorod-like FER-type zeolite

Author: Dai, Weijiong, Ruaux, Valérie, Deng, Xin, Tai, Wenshu, Wu, Guangjun, Guan, Naijia, Li, Landong, Valtchev, Valentin, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), and Valtchev, Valentin
Subjects: [CHIM] Chemical Sciences, [CHIM]Chemical Sciences
Abstract: International audience; Nanosize dimensions have an important impact on zeolite properties and catalytic performance in particular. Herein, we develop a direct synthesis route to obtain nanosized nanorod-like ferrierite (FER) zeolite with the assistance of ammonium fluoride (NH 4 F) and employing a conventional structure-directing agent (Pyrrolidine). The resultant nanorod-like FER zeolite crystals exhibit a greatly reduced diffusion path along the c-axis. The physicochemical properties of nanorod-like FER and its conventional micronsized plate-like counterpart were analyzed by N 2 adsorption-desorption, 27 Al, 1 H, 29 Si MAS NMR, NH 3-TPD, and in situ D 3-acetonitrile and pyridine adsorption followed by FTIR. The nanorod-like FER zeolite possesses superior characteristics in terms of larger external area, better accessibility to the acid sites, and a larger number of pore mouths per unit crystal surface than the micron-sized counterpart synthesized without NH 4 F. The improved properties provide the nanorod-like FER zeolite with high selectivity and low deactivation rates in 1-butene skeletal isomerization. The thermogravimetry analysis (TGA) of the coke amounts revealed a better capability of coke tolerance of the nanorod-like FER zeolite. The in situ Ultraviolet-visible (UV/Vis) and Fourier transform infrared spectroscopy (FTIR) spectroscopy investigations of the organic intermediates formed on FER zeolite catalysts during the catalytic reaction further verified the enhanced catalytic activity and stability of the nanorod-like FER zeolite.
Published: 2021

40. Compatibility between Activity and Selectivity in Catalytic Oxidation of Benzyl Alcohol with Au-Pd Nanoparticles through Redox Switching of SnO

Author: Svetlana Mintova, Peng Bai, Pingping Wu, Lianming Zhao, Yonghui Liu, Chunzheng Wang, Zifeng Yan, Zhengke He, Lei Song, Edgar Muhumuza, China University of Petroleum, IT University of Copenhagen, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: Materials science, 02 engineering and technology, Mesoporous silica, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Redox, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Chemical engineering, Catalytic oxidation, Benzyl alcohol, Oxophilicity, [CHIM]Chemical Sciences, General Materials Science, Partial oxidation, 0210 nano-technology, Selectivity, ComputingMilieux_MISCELLANEOUS
Abstract: A balance between catalytic activity and product selectivity remains a dilemma for the partial oxidation processes because the products are prone to be overoxidized. In this work, we report on the partial oxidation of benzyl alcohol using a modified catalyst consisting of nanosized Au-Pd particles (NPs) with tin oxide (SnOx) deposited on a mesoporous silica support. We found that the SnOx promotes the autogenous reduction of PdO to active Pd0 species on the Au-Pd NP catalyst (SnOx@AP-ox) before H2 reduction, which is due to the high oxophilicity of Sn. The presence of active Pd0 species and the enhancement of oxygen transfer by SnOx led to high catalytic activity. The benzaldehyde selectivity was enhanced with the increase of SnOx content on catalyst SnOx@AP-ox, which is ascribed to the modulated affinity of reactants and products on the catalyst surface through the redox switching of Sn species. After H2 reduction, SnOx was partially reduced and Au-Pd-Sn alloy was formed. The formation of Au-Pd-Sn alloy weakened both the catalytic synergy of Au-Pd alloy NPs and the adsorption of benzyl alcohol on the reduced catalyst, thus leading to low catalytic activity.
Published: 2021
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41. Complex H-bonded silanol network in zeolites revealed by IR and NMR spectroscopy combined with DFT calculations †

Author: Eddy Dib, Izabel Medeiros Costa, Hristiyan A. Aleksandrov, Svetlana Mintova, Georgi N. Vayssilov, 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), University of Sofia, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: 010405 organic chemistry, Renewable Energy, Sustainability and the Environment, Chemistry, Hydrogen bond, Infrared spectroscopy, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Silanol, chemistry.chemical_compound, Phase (matter), Physical chemistry, [CHIM]Chemical Sciences, General Materials Science, Crystallite, Selectivity, Zeolite
Abstract: The amount and location of acid sites (strong Bronsted and weak silanols) in zeolites are crucial for their applications. In this work we revealed the enigma of the complex H-bonded silanol networks in pure silica MFI-type zeolites using 1H solid-state NMR and IR spectroscopy combined with DFT calculations. The silanol sites have a determining role in phase selectivity during the zeolite synthesis and also play an imperative role in setting their acidity, stability, lifetime and hydrophobicity. The spectral signatures of silanol defects in pure silica zeolites are disclosed. Based on the experimental and theoretical observations we identified four types of silanols in pure silica zeolites which varied depending on the crystallite size: (i) isolated (free) silanols, not participating in hydrogen bonds either as proton-donors nor as proton-acceptors, (ii) proton-acceptor silanols, participating in hydrogen bonds only as proton-acceptors, (iii) proton-donor silanols, participating in weak hydrogen bonds and (iv) medium and strong hydrogen-bonding silanols, participating as proton-donors or simultaneously as proton-donors and proton-acceptors. The main factor determining the strength of the hydrogen bond of a specific silanol group is the possibility of its proton to approach closer to the oxygen center of the proton accepting silanol. This suggested that the flexibility of the zeolite fragment at which the proton-donating and proton-accepting silanols are bound is the main factor determining the formation and strength of hydrogen bonds and their corresponding spectral features.
Published: 2021
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42. Isobutane dehydrogenation over high-performanced sulfide V-K/γ-Al 2 O 3 catalyst: modulation of vanadium species and intrinsic effect of potassium

Author: Svetlana Mintova, Ling Wei, Yuanyuan Pan, Alain Rives, Yan-An Liu, Zifeng Yan, Long-li Zhang, Xinmei Liu, Yupeng Tian, China University of Petroleum, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Laboratoire de catalyse de Lille - UMR 8010 (LCL), and Université de Lille, Sciences et Technologies-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: inorganic chemicals, chemistry.chemical_classification, Sulfide, Potassium, Inorganic chemistry, Sulfidation, Vanadium, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Sulfur, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Catalysis, Biomaterials, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Isobutane, [CHIM]Chemical Sciences, Dehydrogenation, 0210 nano-technology
Abstract: Compared with industrial used Pt- and Cr-based catalyst in dehydrogenation (DH) of light alkanes, the sulfide V-K/γ-Al2O3 catalyst reported in this study shows lower cost and toxicity, and significant DH performance. The yield to isobutene reached as high as 52.9%, which is among the highest reported to date. We attribute such high isobutene yield to the precise modulation of polymerization degree for vanadium species via doping of potassium and indicating that the synergy between vanadium species and acid sites is critical to enhance the DH performance. Our previous work showed sulfidation promoted the increase of DH performance for vanadium-based catalyst, and we go further in this study to explore the correlation between increased range of DH performance and the added potassium. The different loaded potassium leads to variation in sulfidation degree, affecting the properties of vanadium species and acid properties consequently. The potassium was distributed uniformly on surface of the sulfide vanadium-based catalyst and was predominantly bonded with the vanadium species rather than with the γ-Al2O3 support. With increasing the potassium amount from 0 to 3 wt%, the acid amount kept decreasing, and some specific strong acid sites appeared once adequate sulfur was introduced in the V-K/γ-Al2O3 catalyst. The characterization and DFT results both revealed that the doped potassium contributes to regulating the vanadium species in the oligomeric state. The synergy between vanadium species and acid properties was regulated by the added potassium simultaneously, and thus the DH performance was enhanced. This study provides promising strategy for preparation of environment-friendly model industrial DH catalyst.
Published: 2021
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43. Interzeolite conversion of a micronsized FAU to a nanosized CHA zeolite free of organic structure directing agent with a high CO2 capacity

Author: Svetlana Mintova, Kristoffer H. Møller, Louwanda Lakiss, Søren Kegnæs, Maxime Debost, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), and Technical University of Denmark [Lyngby] (DTU)
Subjects: Materials science, General Chemical Engineering, High capacity, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Alkali metal, Co2 adsorption, 01 natural sciences, 0104 chemical sciences, Chemical engineering, Organic structure, 0210 nano-technology, Zeolite, Porosity, Chemical composition
Abstract: The interzeolite transformation of a micronsized FAU zeolite to a nanosized CHA zeolite via alkali treatment is presented. The impact of the selection of the FAU zeolite starting material on the properties of the produced CHA zeolite was analyzed by XRD, ICP, SEM, TEM, N2 and CO2 adsorption, and in situ FT-IR. The analysis showed that the choice of starting FAU zeolite had a large impact on the chemical composition, size, morphology, and porosity of the produced CHA zeolite. The as prepared CHA samples show high capacity toward CO2 (4.26 mmol g-1) and it was demonstrated that the chemisorbed vs. physisorbed CO2 was controlled by varying the amount of alkali cations in the CHA zeolite. This journal is
Published: 2020
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44. Incorporation of trivalent cations in NaX zeolite nanocrystals for the adsorption of O2 in the presence of CO2

Author: Sarah Komaty, Michael Badawi, Ayoub Daouli, Samuel Valable, Moussa Zaarour, Svetlana Mintova, Clément Anfray, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS), Université de Lorraine (UL), Laboratoire de Physique et Chimie Théoriques (LPCT), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Imagerie et Stratégies Thérapeutiques des pathologies Cérébrales et Tumorales (ISTCT), Normandie Université (NU)-Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Denticity, Chemistry, [SDV]Life Sciences [q-bio], Inorganic chemistry, General Physics and Astronomy, Infrared spectroscopy, Ionic bonding, Sorption, 02 engineering and technology, Faujasite, engineering.material, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Adsorption, Physisorption, 13. Climate action, engineering, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, Zeolite
Abstract: CERVOXY COLL; International audience; The O2 and CO2 sorption properties of nanosized zeolite X with faujasite type structure through a partial ionic exchange of sodium (Na +) by trivalent cations (Gd 3+ and Ce 3+) were evaluated. Three faujasite samples were studied, the as-synthesized Na-X possessing Na + solely, and the modified samples Na-Gd-X and Na-Ce-X containing Gd 3+ (1.8 wt%) and Ce 3+ (0.82 wt%), respectively. Incorporating scarce amounts of trivalent cations modified the adsorption affinity of zeolites towards O2 and CO2 as demonstrated by in situ Fourier-transform infrared spectroscopy (FTIR). While Na-Ce-X encounters the highest O2 physisorption capacity, the Na-Gd-X is adsorbing the highest quantities of molecular CO2. All three samples exhibit the chemisorbed CO2 in the form of carbonates, while the Na-X stores carbonates in monodentate and polydentate forms, the Na-Gd-X and Na-Ce-X allow the formation of polydentate carbonates only. Density functional theory (DFT) calculations revealed that trivalent cations tend to adsorb gases through two cations simultaneously which explains the presence of polydentate carbonates exclusively in the corresponding modified zeolites. The DFT results confirmed the higher affinity of Na-Gd-X and Na-Ce-X nanocrystals towards O2 in the presence of CO2. The affinity of Na-Gd-X and Na-Ce-X nanocrystals towards O2 opens the door of their use as oxygen transporters for medical applications where CO2 is constantly present. The toxicity of the nanosized zeolites and their performance in O2 release are reported too.
Published: 2020
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45. A sponge-like small pore zeolite with great accessibility to its micropores

Author: Lingxue Tang, Kok-Giap Haw, Valentin Valtchev, Zhengxing Qin, Qianrong Fang, Simona Moldovan, Shilun Qiu, Jilin University (JLU), Groupe de physique des matériaux (GPM), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-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)-Institut de Recherche sur les Matériaux Avancés (IRMA), 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)-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)-Université de Caen Normandie (UNICAEN), 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), China University of Petroleum, Laboratoire catalyse et spectrochimie (LCS), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-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)-Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), and Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN)
Subjects: Materials science, Macropore, 02 engineering and technology, Microporous material, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystal, Crystallinity, Chemical engineering, Physisorption, Specific surface area, [CHIM]Chemical Sciences, 0210 nano-technology, Zeolite, Dissolution
Abstract: International audience; Small pore zeolites, due to pore size constraint, have limited applications. Post-modification on the materials is therefore important to widen their use. A CHA-type zeolite (SSZ-13) with unique sponge-like structure is obtained by fluoride leaching. The development of macroporosity started from the crystal surfaces and continued progressively into the crystal by prolonging treatment. Nitrogen physisorption measurements showed an increase in micropore volume and specific surface area as a consequence of the dissolution of low crystalline part of the zeolite. The impact of etching on the accessiblity through the pore network, evaluated by means of breakthrough experiments of CO2/N2 and CO2/CH4 binary mixtures, showed an improved accessibility thanks to the interconnected macropores which shortens the diffusion pathlength. The set of experimental data shows the sponge-like SSZ-13 crystals retaining the intrinsic zeolitic properties but having an improve accessibility and crystallinity.
Published: 2020
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46. Breaking the Si/Al Limit of Nanosized β Zeolites: Promoting Catalytic Production of Lactide

Author: Jing Shi, Binju Wang, Qing Zhang, Qiang Zhang, Osamu Terasaki, Jihong Yu, Jun Luo, Yinghao Liu, Weiyan Liu, Xuesi Chen, Jean-Pierre Gilson, Sheng Xiang, Alvaro Mayoral, Guoju Yang, Yuyao Wang, State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, Jilin University, Chongqing University [Chongqing], CINTRA / SEEE Nanyang Technological University, Nanyang Technological University [Singapour], Xiamen University, Laboratorio de microscopias avanzadas (LMA), University of Zaragoza - Universidad de Zaragoza [Zaragoza], SHANGAI UNIVERSITY, Jilin University, Khalifa University, College of Informatics [Wuhan Hubei], Huazhong Agricultural University, Changchun Institute of Technology, Structural Chemistry, Arrhenius Laboratory (STRUCTURAL CHEMISTRY), Stockholm University, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Laboratoire de Recherche en Informatique (LRI), and CentraleSupélec-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Condensation polymer, Lactide, General Chemical Engineering, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Lactic acid, Amino acid, Catalysis, chemistry.chemical_compound, chemistry, Polylactic acid, Chemical engineering, Materials Chemistry, [CHIM]Chemical Sciences, Methanol, 0210 nano-technology, Zeolite, ComputingMilieux_MISCELLANEOUS
Abstract: Efficient production of lactide (LT) from highly concentrated lactic acid (LA) based on β zeolite catalysts is highly desired for an economically sustainable polylactic acid (PLA) industry. Like an...
Published: 2019
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47. Magnetic Fe@Y Composites as Efficient Recoverable Catalysts for the Valorization of the Recalcitrant Marine Sulfated Polysaccharide Ulvan

Author: Vassilios Roussis, Jan Přech, Victor Kuncser, Iunia Podolean, Valentin Valtchev, Efstathia Ioannou, Simona M. Coman, Vasile I. Parvulescu, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), National and Kapodistrian University of Athens (NKUA), and University of Bucharest (UniBuc)
Subjects: magnetic nanoparticles, oxidation, General Chemical Engineering, Nanoparticle, 02 engineering and technology, 010402 general chemistry, Polysaccharide, 7. Clean energy, 01 natural sciences, Catalysis, Hydrolysis, ulvan, Sulfation, Environmental Chemistry, Composite material, Zeolite, chemistry.chemical_classification, Renewable Energy, Sustainability and the Environment, Y zeolite, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, equipment and supplies, 021001 nanoscience & nanotechnology, 0104 chemical sciences, hydrolysis, chemistry, Magnetic nanoparticles, 0210 nano-technology, human activities
Abstract: International audience; Magnetic Fe@Y composites (carbon coated magnetic iron nanoparticles incorporated in Y zeolite) with 5-8 wt% Fe were synthesized and characterized. Overall acidity of the samples ranges between 2.0 and 2.47 mmol/g and is given mostly by Lewis acid sites. The obtained materials were proven to catalyze the hydrolysis of Ulvan polysaccharide with high conversions. The distribution of the reaction products depends on the reaction conditions and the concentration of Ulvan. The catalytic properties-catalytic performances correlations clearly show the acid zeolite Y is the active phase for Ulvan hydrolysis while the iron nanoparticles enable the catalyst separation in a magnetic field. Under oxygen pressure, the selectivity was completely changed to succinic acid. All Fe@Y composites were recycled for 10 times with no change in the catalytic performances after a simple magnetic separation and washing with water.
Published: 2019
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48. Selective catalytic reduction of NOx over Cu- and Fe-exchanged zeolites and their mechanical mixture

Author: Houeida Issa Hamoud, Valentin Valtchev, Marco Daturi, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: Inorganic chemistry, composite catalysts, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Ammonia, chemistry.chemical_compound, Transition metal, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, metal exchanged zeolites, SAPO-34, [CHIM]Chemical Sciences, Fourier transform infrared spectroscopy, ComputingMilieux_MISCELLANEOUS, NOx, General Environmental Science, Chemistry, Process Chemistry and Technology, Cationic polymerization, Selective catalytic reduction, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, Atmospheric temperature range, 021001 nanoscience & nanotechnology, Mordenite, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, NH3-SCR, 0210 nano-technology
Abstract: International audience; SCR-NH3 activities of Cu-SAPO-34 (Cu-CZC) and Fe-Mordenite (Fe-MOR) and their mechanical mixture (50:50) were investigated in the temperature range 150-450 °C using operando FTIR spectroscopy. Structural and textural studies assessed the quality of the material synthesis, while in situ IR characterisation allowed the quantification of the acidic sites at the surface of the zeolites, as well as the cationic distribution inside the pores. As expected, Cu-CZC showed high NOx activity at lower temperatures (75 % of NOx conversion at T < 300 °C), while Fe-MOR was more active (> 85 %) at higher temperatures (300-450 °C). The co-presence of Cu and Fe in the mechanical mixture catalyzes the undesirable oxidation of ammonia and leads to the formation of NO, especially at high temperatures. However, the mechanical mixture of Cu-CZC and Fe-MOR has been found to efficiently operate in the presence of excess ammonia (NH3/NOx = 1.3) in a much broader temperature range comparing to the catalysts modified with only one transition metal (Fe or Cu) and also respect to a sample containing both cations in a single zeolitic framework, thus opening new opportunities in the catalytic reduction of NOx.
Published: 2019
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49. Preparation of Single-Crystal 'House-of-Cards'-like ZSM-5 and Their Performance in Ethanol-to-Hydrocarbon Conversion

Author: T. Jean Daou, Jean-Pierre Gilson, Ovidiu Ersen, Ludovic Pinard, Mohammed Amine Benghalem, Shunsuke Asahina, Valentin Valtchev, Georgian Melinte, Zhengxing Qin, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), 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, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)
Subjects: chemistry.chemical_classification, Ethanol, Materials science, General Chemical Engineering, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Isotropic etching, 0104 chemical sciences, chemistry.chemical_compound, Hydrocarbon, Chemical engineering, chemistry, Materials Chemistry, [CHIM]Chemical Sciences, ZSM-5, 0210 nano-technology, Single crystal, ComputingMilieux_MISCELLANEOUS
Abstract: The present study reports the unbiased chemical etching of micron-sized ZSM-5 crystals with an NH4F solution, resulting in house-of-cards-like single crystals containing large rectangular cavities ...
Published: 2019
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50. Direct Evidence for Single Molybdenum Atoms Incorporated in the Framework of MFI Zeolite Nanocrystals

Author: Jean-Pierre Gilson, Delphine Minoux, Florent Dubray, Svetlana Mintova, Cassandre Kouvatas, Julien Grand, Cindy Aquino, Simona Moldovan, Nicolas Barrier, Nikolai Nesterenko, Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace, Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-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))-Université de Strasbourg (UNISTRA), Total Research and Technology Feluy ( [TRTF]), Laboratoire de physique des océans (LPO), and Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Molybdenum, Direct evidence, chemistry.chemical_element, Oxides, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Colloid and Surface Chemistry, chemistry, Chemical engineering, Nanocrystal, Homogeneous, Zeolites, [CHIM]Chemical Sciences, Zeolite, Materials, Nuclear magnetic resonance spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Direct evidence of the successful incorporation of atomically dispersed molybdenum (Mo) atoms into the framework of nanosized MFI zeolite is demonstrated for the first time. Homogeneous distribution of Mo with a size of 0.05 nm is observed by scanning transmission electron microscopy high-angle annular dark-field imaging (STEM-HAADF). 31P magic-angle spinning nuclear magnetic resonance (MAS NMR) and Fourier-transform infrared (FT-IR) spectroscopy, using trimethylphosphine oxide (TMPO) and deuterated acetonitrile as probe molecules, reveal a homogeneous distribution of Mo in the framework of MFI nanozeolite, and the presence of Lewis acidity. 31P MAS NMR using TMPO shows probe molecules interacting with isolated Mo atoms in the framework, and physisorbed probe molecules in the zeolite channels. Moreover, 2D 31P–31P MAS radio frequency-driven recoupling NMR indicates the presence of one type of Mo species in different crystallographic positions in the MFI framework. The substitution of framework Si by Mo significantly reduces the silanol defect content, making the resulting zeolite highly hydrophobic. In addition, the insertion of Mo into the MFI structure induces a symmetry lowering, from orthorhombic (Pnma), typical of high silica MFI, to monoclinic (P21/n), as well as an expansion of unit cell volume. The novel material opens many opportunities of catalysts design for application in mature and emerging fields
Published: 2019
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