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Reduction of dinitrogen by molybdenum nitrogenase relies on complex metalloclusters: the [8Fe:7S] P-cluster and the [7Fe:9S:Mo:C:homocitrate] FeMo-cofactor. Although both clusters bear topological similarities and require the reductive fusion of [4Fe:4S] sub-clusters to achieve their respective assemblies, P-clusters are assembled directly on the NifD(2)K(2) polypeptide prior to the insertion of FeMo-co, which is fully assembled separately from NifD(2)K(2). P-cluster maturation involves the iron protein NifH(2) as well as several accessory proteins, whose role has not been elucidated. In the present work, two NifD(2)K(2) species bearing immature P-clusters were isolated from an Azotobacter vinelandii strain in which the genes encoding NifH and the accessory protein NifZ were deleted, and characterized by X-ray absorption spectroscopy and EPR. These analyses showed that both NifD(2)K(2) complexes harbor clusters that are electronically and structurally similar, with each NifDK unit containing two [4Fe:4S](2+/+) clusters. Binding of the accessory protein NifW parallels a decrease in the distance between these clusters, as well as a subtle change in their coordination. These results support a conformational role for NifW in P-cluster biosynthesis, bringing the two [4Fe:4S] precursors closer prior to their fusion, which may be crucial in challenging cellular contexts. Max-Planck Society; DFG SPP 1927 "Iron-Sulfur for Life" [DE 1877/1-1]; Peter und Traudl Engelhorn Stiftung; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-76SF00515]; Bill and Melinda Gates Foundation grant BNF Cereals Phase II [OPP1143172]; Bill and Melinda Gates Foundation grant BNF Cereals Phase III [INV-005889]; U.S. Department of Energy, Office of Science, Basic Energy Science [DE-SC0010834, DE-SC0010867]; Bill & Melinda Gates Foundation [OPP1143172, INV-005889] Published version C. V. S., S. D., and L. D. would like to thank the Max-Planck Society for funding. S. D. and C. V. S. acknowledge the DFG SPP 1927 "Iron-Sulfur for Life" (project DE 1877/1-1) for funding. L. D. thanks the Peter und Traudl Engelhorn Sti.ung for funding. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. C. V. S., S. D., and L. D. gratefully acknowledge Matthew Latimer for his technical assistance during XAS measurements at beamline 9-3. George E. Cutsail III, Justin H. Henthorn, and Patricia Rodr ' iguez Mac ' ia are also thanked for their assistance in XAS data collection. E. J.-V. and A. P. G. were supported by Bill and Melinda Gates Foundation grants BNF Cereals Phase II (OPP1143172) and BNF Cereals Phase III (INV-005889). Work in the laboratories of L. C. S and D. R. D. is supported by grants from the U.S. Department of Energy, Office of Science, Basic Energy Science, DE-SC0010834 and DE-SC0010867, respectively. This work was supported, in whole or in part, by the Bill & Melinda Gates Foundation (OPP1143172, INV-005889). Under the grant conditions of the Foundation, a Creative Commons Attribution 4.0 Generic License has already been assigned to the Author Accepted Manuscript version that might arise from this submission.

The intrinsic stability of the 5 V LiCoPO4-LiCo2P3O10 thin-film (carbon-free) cathode material coated with MoO3 thin layer is studied using a comprehensive synchrotron electron spectroscopy in situ approach combined with firstprinciple calculations. The atomic-molecular level study demonstrates fully reversible electronic properties of the cathode after the first electrochemical cycle. The polyanionic oxide is not involved in chemical reactions with the tluoroethylene-containing liquid electrolyte even when charged to 5.1 V vs Li+/Li. The high stability of the cathode is explained on the basis of the developed energy level model. In contrast, the chemical composition of the cathode-electrolyte interface evolves continuously by involving MoO3 in the decomposition reaction with consequent leaching of oxide from the surface. The proposed mechanisms of chemical reactions are attributed to external electrolyte oxidation via charge transfer from the relevant electron level to the MoO3 valence band state and internal electrolyte oxidation via proton transfer to the solvents. This study provides a deeper insight into the development of both a doping strategy to enhance the electronic conductivity of high-voltage cathode materials and an efficient surface coating against unfavorable interfacial chemical reactions.

We report femtosecond Fe K-edge absorption (XAS) and nonresonant X-ray emission (XES) spectra of ferric cytochrome C (Cyt c) upon excitation of the haem (>300 nm) or mixed excitation of the haem and tryptophan (

Oxycodone is a strong opioid frequently used as an analgesic. Although proven efficacious in the management of moderate to severe acute pain and cancer pain, use of oxycodone imposes a risk of adverse effects such as addiction, overdose, and death. Fast and accurate determination of oxycodone blood concentration would enable personalized dosing and monitoring of the analgesic as well as quick diagnostics of possible overdose in emergency care. However, in addition to the parent drug, several metabolites are always present in the blood after a dose of oxycodone, and to date, there is no electrochemical data available on any of these metabolites. In this paper, a single-walled carbon nanotube (SWCNT) electrode and a Nafion-coated SWCNT electrode were used, for the first time, to study the electrochemical behavior of oxycodone and its two main metabolites, noroxycodone and oxymorphone. Both electrode types could selectively detect oxycodone in the presence of noroxycodone and oxymorphone. However, we have previously shown that addition of a Nafion coating on top of the SWCNT electrode is essential for direct measurements in complex biological matrices. Thus, the Nafion/SWCNT electrode was further characterized and used for measuring clinically relevant concentrations of oxycodone in buffer solution. The limit of detection for oxycodone with the Nafion/SWCNT sensor was 85 nM, and the linear range was 0.5-10 mu M in buffer solution. This study shows that the fabricated Nafion/SWCNT sensor has potential to be applied in clinical concentration measurements.

Titania-supported vanadia (VOx/TiO2) catalysts exhibit outstanding catalytic in a number of selective oxidation and reduction processes. In spite of numerous investigations, the nature of redox transformations of vanadium and titanium involved in various catalytic processes remains difficult to detect and correlate to the rate of products formation. In this work, we studied the redox dynamics of active sites in a bilayered 5% V2O5/15% TiO2/SiO2 catalyst (consisting of submonolayer VOx species anchored onto a TiOx monolayer, which in turn is supported on SiO2) during the oxidative dehydrogenation of ethanol. The VOx species in 5% V2O5/15% TiO2/SiO2 show high selectivity to acetaldehyde and an ca. 40 times higher acetaldehyde formation rate in comparison to VOx species supported on SiO2 with a similar density. Operando time-resolved V and Ti K-edge X-ray absorption near-edge spectroscopy, coupled with a transient experimental strategy, quantitatively showed that the formation of acetaldehyde over 5% V2O5/15% TiO2/SiO2 is kinetically coupled to the formation of a V4+ intermediate, while the formation of V3+ is delayed and 10–70 times slower. The low-coordinated nature of various redox states of VOx species (V5+, V4+, and V3+) in the 5% V2O5/15% TiO2/SiO2 catalyst is confirmed using the extensive database of V K-edge XANES spectra of standards and specially synthesized molecular crystals. Much weaker redox activity of the Ti4+/Ti3+ couple was also detected; however, it was found to not be kinetically coupled to the rate-determining step of ethanol oxidation. Thus, the promoter effect of TiOx is rather complex. TiOx species might be involved in a fast electron transport between VOx species and might affect the electronic structure of VOx, thereby promoting their reducibility. This study demonstrates the high potential of element-specific operando X-ray absorption spectroscopy for uncovering complex catalytic mechanisms involving the redox kinetics of various metal oxides., JACS Au, 2 (3), ISSN:2691-3704

Selenium (Se) is a toxic contaminant with multiple anthropogenic sources, including 79Se from nuclear fission. Se mobility in the geosphere is generally governed by its oxidation state, therefore understanding Se speciation under variable redox conditions is important for the safe management of Se contaminated sites. Here, we investigate Se behavior in sediment groundwater column systems. Experiments were conducted with environmentally relevant Se concentrations, using a range of groundwater compositions, and the impact of electron-donor (i.e., biostimulation) and groundwater sulfate addition was examined over a period of 170 days. X-Ray Absorption Spectroscopy and standard geochemical techniques were used to track changes in sediment associated Se concentration and speciation. Electron-donor amended systems with and without added sulfate retained up to 90% of added Se(VI)(aq), with sediment associated Se speciation dominated by trigonal Se(0) and possibly trace Se(-II); no Se colloid formation was observed. The remobilization potential of the sediment associated Se species was then tested in reoxidation and seawater intrusion perturbation experiments. In all treatments, sediment associated Se (i.e., trigonal Se(0)) was largely resistant to remobilization over the timescale of the experiments (170 days). However, in the perturbation experiments, less Se was remobilized from sulfidic sediments, suggesting that previous sulfate-reducing conditions may buffer Se against remobilization and migration.

Many-electron multiconfigurational ab initio calculations are combined with x-ray spectroscopy to scrutinize a popular model for electron transfer in lanthanide-doped crystals which hypothesizes that the electrons are conveyed by the conduction band of the host. Contrary to this accepted picture, our combined theoretical-experimental effort shows that the reversible electron phototransfer from Eu2+ to Sm3+ in CaF2 is direct, from metal to metal. It is theoretically predicted and experimentally verified that visible light induces the reverse electron transfer.

Chemical composition of interfaces between physical-vapor-deposited TiN and SiO2 as affected by introduction of a thin (0.5–3 nm) alumina interlayer was studied using photoelectron spectroscopy wit...

This study aims at assessing the thermal nuclei motion effects on the multipole transition channels involved in two core-level spectroscopies, x-ray absorption spectroscopy (XAS) and x-ray Raman scattering (XRS). Temperature effects on the $1s\ensuremath{\rightarrow}s$ monopole, $1s\ensuremath{\rightarrow}p$ dipole, and $1s\ensuremath{\rightarrow}d$ quadrupole transitions are investigated using two reference systems for which we present original experimental data: $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Al}}_{2}{\mathrm{O}}_{3}$ at the Al $K$ edge probed by XRS at room temperature and rutile $\mathrm{Ti}{\mathrm{O}}_{2}$ at the Ti $K$ pre-edge probed by XAS at temperatures ranging from 6 to 700 K. Through the latter, this work enlightens the part of the pre-edge peak enhancement due to temperature in the $K$ pre-edge region of $3d$ transition metal, which is known to be routinely used to determine the concentration, valence or symmetry of the probed element in a given sample. Nuclear thermal fluctuations are taken into account using a method based on density functional theory that consists in averaging spectra over atomic configurations, generated within the harmonic approximation and obeying quantum statistics at finite temperature. Since only a finite number of such configurations are used, the numerically averaged spectra generally lose the symmetry of the equilibrium crystal positions. In this paper, we demonstrate that the physical average has to be symmetric and propose a method to restore the physical angular dependence of the spectra. The approach is successfully applied to investigate the angular dependent XAS spectra in rutile as a function of temperature. The two systems under study allow to draw general conclusions regarding the effect of nuclear quantum fluctuations on the different transition channels available to both core-level spectroscopies.

ispartof: ADVANCED SUSTAINABLE SYSTEMS vol:6 issue:8 status: published

Physical chemistry, chemical physics 22(36), 20311 - 20330 (1-20) (2020). doi:10.1039/D0CP04033A, Permanganate aqueous solutions, MnO$_4$$^-$(aq.), were studied using liquid-micro-jet-based soft X-ray non-resonant and resonant photoelectron spectroscopy to determine valence and core-level binding energies. To identify possible differences in the energetics between the aqueous bulk and the solution-gas interface, non-resonant spectra were recorded at two different probing depths. Similar experiments were performed with different counter ions, Na$^+$ and K$^+$, with the two solutions yielding indistinguishable anion electron binding energies. Our resonant photoelectron spectroscopy measurements, performed near the Mn L$_{II,III}$- and O K-edges, selectively probed valence charge distributions between the Mn metal center, O ligands, and first solvation shell in the aqueous bulk. Associated resonantly-enhanced solute ionisation signals revealed hybridisation of the solute constituents’ atomic orbitals, including the inner valence Mn 3p and O 2s. We identified intermolecular Coulombic decay relaxation processes following resonant X-ray excitation of the solute that highlight valence MnO$_4$$^-$$_{(aq.)}$-H$_2$O$_{(l)}$ electronic couplings. Furthermore, our results allowed us to infer oxidative reorganisation energies of MnO$_4$$^•$$_{(aq.)}$ and adiabatic valence ionisation energies of MnO$_4$$^-$$_{(aq.)}$, revealing the Gibbs free energy of oxidation and permitting estimation of the vertical electron affinity of MnO$_4$$^•$$_{(aq.)}$. Finally, the Gibbs free energy of hydration of isolated MnO$_4$$^-$ was determined. Our results and analysis allowed a near-complete binding-energy-scaled MnO$_4$$^-$$_{(aq.)}$ molecular orbital and a valence energy level diagram to be produced for the MnO$_4$$^-$$_{(aq.)}$ / MnO$_4$$^•$$_{(aq.)}$ system. Cumulatively, our mapping of the aqueous-phase electronic structure of MnO$_4$$^-$ is expected to contribute to a deeper understanding of the exceptional redox properties of this widely applied aqueous transition-metal complex ion., Published by RSC Publ., Cambridge

By use of a combination of electrical measurements and internal photoemission interface barrier characterization, the effective workfunction (EWF) changes of nm-thin TiN layer deposited on top of o...

Simultaneous retention of SMM behaviour and of optical activity is demonstrated upon surface deposition for a chiral SMM., The synthesis and characterization of a chiral, enneanuclear Mn(iii)-based, Single-Molecule Magnet, [Mn9O4(Me-sao)6(L)3(MeO)3(MeOH)3]Cl (1; Me-saoH2 = methylsalicylaldoxime, HL = lipoic acid) is reported. Compound 1 crystallizes in the orthorhombic P212121 space group and consists of a metallic skeleton describing a defect super-tetrahedron missing one vertex. The chirality of the [MnIII9] core originates from the directional bridging of the Me-sao2– ligands via the –N–O– oximate moieties, which define a clockwise (1ΔΔ) or counter-clockwise (1ΛΛ) rotation in both the upper [MnIII3] and lower [MnIII6] subunits. Structural integrity and retention of chirality upon dissolution and upon deposition on (a) gold nanoparticles, 1@AuNPs, (b) transparent Au(111) surfaces, 1ΛΛ@t-Au(111); 1ΔΔ@t-Au(111), and (c) epitaxial Au(111) on mica surfaces, 1@e-Au(111), was confirmed by CD and IR spectroscopies, mass spectrometry, TEM, XPS, XAS, and AFM. Magnetic susceptibility and magnetization measurements demonstrate the simultaneous retention of SMM behaviour and optical activity, from the solid state, via dissolution, to the surface deposited species.

Simulations based on density functional theory (DFT) were used to investigate the behaviour of substitutional iron in both tetragonal and monoclinic ZrO2. Brouwer diagrams of predicted defect concentrations, as a function of oxygen partial pressure, suggest that iron behaves as a p-type dopant in monoclinic ZrO2 while it binds strongly to oxygen vacancies in tetragonal ZrO2. Analysis of defect relaxation volumes suggest that these results should hold true in thermally grown oxides on zirconium, which is under compressive stresses. X-ray absorption near edge structure (XANES) measurements, performed to determine the oxidation state of iron in Zircaloy-4 oxide samples, revealed that 3 + is the favourable oxidation state but with between a third and half of the iron, still in the metallic Fe0 state. The DFT calculations on bulk zirconia agree with the preferred oxidation state of iron if it is a substitutional species but do not predict the presence of metallic iron in the oxide. The implications of these results with respect to the corrosion and hydrogen pick-up of zirconium cladding are discussed.

All-solid-state batteries promise significant safety and energy density advantages over liquid-electrolyte batteries. The interface between the cathode and the solid electrolyte is an important contributor to charge transfer resistance. Strong bonding of solid oxide electrolytes and cathodes requires sintering at elevated temperatures. Knowledge of the temperature dependence of the composition and charge transfer properties of this interface is important for determining the ideal sintering conditions. To understand the interfacial decomposition processes and their onset temperatures, model systems of LiCoO2 (LCO) thin films deposited on cubic Al-doped Li7La3Zr2O12 (LLZO) pellets were studied as a function of temperature using interface-sensitive techniques. X-ray photoelectron spectroscopy (XPS), secondary ion mass spectroscopy (SIMS), and energy-dispersive X-ray spectroscopy (EDS) data indicated significant cation interdiffusion and structural changes starting at temperatures as low as 300°C. La2Zr2O7 and Li2CO3 were identified as decomposition products after annealing at 500°C by synchrotron X-ray diffraction (XRD). X-ray absorption spectroscopy (XAS) results indicate the presence of also LaCoO3, in addition to La2Zr2O7 and Li2CO3. Based on electrochemical impedance spectroscopy, and depth profiling of the Li distribution upon potentiostatic hold experiments on symmetric LCO|LLZO|LCO cells, the interfaces exhibited significantly increased impedance, up to 8 times that of the as-deposited samples after annealing at 500°C. Our results indicate that lower-temperature processing conditions, shorter annealing time scales, and CO2-free environments are desirable for obtaining ceramic cathode-electrolyte interfaces that enable fast Li transfer and high capacity.

We present results of combined experimental photoelectron spectroscopy and theoretical modeling studies of solvated dicarboxylate species (-O2C(CH2)2CO2-) in complex with Na+ and K+ metal cations. These ternary clusters serve as simple models for the investigation of aqueous ion/solute specific effects that play an important role in biological systems. The experimental characterization of these systems was performed in the presence of up to six solvating waters. In both Na+ and K+ cases, we observe the presence of one major broad band that gradually shifts to higher electron binding energy (EBE) with an increasing number of waters. In the Na+ case further detailed analysis of experimental spectra was performed using ab initio calculations. In particular, we have identified the structures of the lowest energy clusters whose EBE values match well the major band in the experimental spectra. Our results show that evolution of an aqueous solvation shell emphasizes the coordination of the negatively charged carboxylate groups accompanied by simultaneous interaction with metal cations. Calculations also indicate that in the solvation range investigated experimentally (up to 6 waters), Na+ retains direct contact with the dicarboxylate species, i.e. a contact ion-pair (CIP) complex. Preliminary modeling studies show evidence of an alternative solvent separated ion-pair complex once the solvation range approaches 8 waters, however its energy still remains above that of (∼7-8 kcal/ mol-1) the CIP complex. At a higher number of waters (n = 3 for Na+ and n = 5 for K+), the experimental spectra also show the development of a weak low energy band. Its origin cannot be precisely identified. Our calculations in the Na+ case point out the existence of a quaternary complex consisting of Na+, H2O, OH- and a singly protonated dicarboxylate anion (HO2C(CH)2CO2-). Such a complex appears to be stabilized in the solvation range corresponding to the appearance of the low EBE band and does match its peak, even though the energy of such a complex is fairly high compared to the ternary structure. ispartof: PHYSICAL CHEMISTRY CHEMICAL PHYSICS vol:20 issue:46 pages:29051-29060 ispartof: location:England status: published

Cost‐effective and environment‐friendly aqueous zinc‐ion batteries (AZIBs) exhibit tremendous potential for application in grid‐scale energy storage systems but are limited by suitable cathode materials. Hydrated vanadium bronzes have gained significant attention for AZIBs and can be produced with a range of different pre‐intercalated ions, allowing their properties to be optimized. However, gaining a detailed understanding of the energy storage mechanisms within these cathode materials remains a great challenge due to their complex crystallographic frameworks, limiting rational design from the perspective of enhanced Zn2+ diffusion over multiple length scales. Herein, a new class of hydrated porous δ‐Ni0.25V2O5.nH2O nanoribbons for use as an AZIB cathode is reported. The cathode delivers reversibility showing 402 mAh g−1 at 0.2 A g−1 and a capacity retention of 98% over 1200 cycles at 5 A g−1. A detailed investigation using experimental and computational approaches reveal that the host “δ” vanadate lattice has favorable Zn2+ diffusion properties, arising from the atomic‐level structure of the well‐defined lattice channels. Furthermore, the microstructure of the as‐prepared cathodes is examined using multi‐length scale X‐ray computed tomography for the first time in AZIBs and the effective diffusion coefficient is obtained by image‐based modeling, illustrating favorable porosity and satisfactory tortuosity.

Iron phthalocyanines (FePc) adsorbed onto a Ag(110) substrate self-assemble into different monolayer phases going from rectangular to different oblique phases, with increasing molecular density. We have investigated the oxygen uptake capability of the different phases and their associated magneto-structural changes. Our study combines scanning tunneling microscopy and spectroscopy (STM/STS), X-ray magnetic circular dichroism (XMCD), and density functional theory (DFT) calculations. STM measurements reveal that the oxygenation reaction of the FePc/Ag(110) generally involves a displacement and a rotation of the molecules, which affects the electronic state of the Fe centers. The oxygen intercalation between FePc and the substrate is greatly obstructed by the steric hindrance in the high-density phases, to the point that a fraction of oblique phase molecules cannot change their position after oxidizing. Depending on the oxidation state and adsoption geometry, the STS spectra show clear differences in the Fe local density of states, which are mirrored in the XAS and XMCD experiments. Particularly, XMCD spectra of the oxidized phases reflect the distribution of FePc species (nonoxygenated, oxygenated-rotated, and oxygenated-unrotated) in the different cases. Sum rule analysis yields the effective spin (mseff) and orbital (mL) magnetic moments of Fe in the different FePc species. Upon oxygenation, the magnetic moment of FePc molecules increases about an order of magnitude, reaching mTOT ∼ 2.2 μB per Fe atom., We acknowledge financial support from the Spanish MCINN Project (DWARFS MAT2017-83468-R) and the Aragonese Projects E12-17R RASMIA and E09-17R Q-MAD (co-funded by Fondo Social Europeo), and of the European Union FEDER (ES); from the University of Padova Grant CPDA154322 AMNES, and from the European Regional Development Fund (ERDF) under the program Interreg V-A España-Francia-Andorra (Contract EFA 194/16 TNSI). M.P. and A.M. are funded by the CERCA Program/Generalitat de Catalunya and the Severo Ochoa program from Spanish MINECO (Grant SEV-2017-0706).

Photodissociation regions (PDRs) are parts of the ISM consisting of predominantly neutral gas, located at the interface between H II regions and molecular clouds. The physical conditions within these regions show variations on very short spatial scales, and therefore PDRs constitute ideal laboratories for investigating the properties and evolution of dust grains. We have mapped IC 63 at high resolution from the UV to the NIR (275 nm to 1.6 $\mu$m), using the Hubble Space Telescope WFC3. Using a Bayesian SED fitting tool, we simultaneously derive a set of stellar ($T_\text{eff}$, $\log(g)$, distance) and extinction ($A_V$, $R_V$) parameters for 520 background stars. We present maps of $A_V$ and $R_V$ with a resolution of 25 arcsec based on these results. The extinction properties vary across the PDR, with values for $A_V$ between 0.5 and 1.4 mag, and a decreasing trend in $R_V$, going from 3.7 at the front of the nebula to values as low as 2.5 further in. This provides evidence for evolution of the dust optical properties. We fit two modified blackbodies to the MIR and FIR SED, obtained by combining the $A_V$ map with data from Spitzer and Herschel. We derive effective temperatures (30 K and 227 K) and the ratio of opacities at 160 $\mu$m to V band $\kappa_{160} / \kappa_V$ ($7.0 \times 10^{-4}$ and $2.9 \times 10^{-9}$) for the two dust populations. Similar fits to individual pixels show spatial variations of $\kappa_{160} / \kappa_{V}$. The analysis of our HST data, combined with these Spitzer and Herschel data, provides the first panchromatic view of dust within a PDR., Comment: 28 pages, 20 figures, accepted for publication in The Astrophysical Journal

Laser excitation and x-ray spectroscopy are combined to settle a long-standing question in persistent luminescence. A reversible electron transfer is demonstrated, controlled by light and showing the same kinetics as the persistent luminescence. Exposure to violet light induces charging by oxidation of the excited Eu2+ while Dy3+ is simultaneously reduced. Oppositely, detrapping of Dy2+ occurs at ambient temperature or by infrared illumination, yielding afterglow or optically stimulated luminescence, respectively.

Energy storage solutions are a vital component of the global transition toward renewable energy sources. The power-to-gas (PtG) concept, which stores surplus renewable energy in the form of methane, has therefore become increasingly relevant in recent years. At present, supported Ni nanoparticles are preferred as industrial catalysts for CO2 methanation due to their low cost and high methane selectivity. However, commercial Ni catalysts are not active enough in CO2 methanation to reach the high CO2 conversion (>99%) required by the specifications for injection in the natural gas grid. Herein we demonstrate the promise of promotion of Ni by Mn, another low-cost base metal, for obtaining very active CO2 methanation catalysts, with results comparable to more expensive precious metal-based catalysts. The origin of this improved performance is revealed by a combined approach of nanoscale characterization, mechanistic study, and density functional theory calculations. Nanoscale characterization with scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy (STEM-EDX) and X-ray absorption spectroscopy shows that NiMn catalysts consist of metallic Ni particles decorated by oxidic Mn2+ species. A mechanistic study combining IR spectroscopy of surface adsorbates, transient kinetic analysis with isotopically labeled CO2, density functional theory calculations, and microkinetics simulations ascertains that the MnO clusters enhance CO2 adsorption and facilitate CO2 activation. A macroscale perspective was achieved by simulating the Ni and NiMn catalytic activity in a Sabatier reactor, which revealed that NiMn catalysts have the potential to meet the demanding PtG catalyst performance requirements and can largely replace the need for expensive and scarce noble metal catalysts.

The atomic contributions to valence electronic structure for 37 ionic liquids (ILs) are identified using a combination of variable photon energy XPS, resonant Auger electron spectroscopy (RAES) and a subtraction method. The ILs studied include a diverse range of cationic and anionic structural moieties. We introduce a new parameter for ILs, the energy difference between the energies of the cationic and anionic highest occupied fragment orbitals (HOFOs), which we use to identify the highest occupied molecular orbital (HOMO). The anion gave rise to the HOMO for 25 of the 37 ILs studied here. For 10 of the ILs, the energies of the cationic and anionic HOFOs were the same (within experimental error); therefore, it could not be determined whether the HOMO was from the cation or the anion. For two of the ILs, the HOMO was from the cation and not from the anion; consequently it is energetically more favourable to remove an electron from the cation than the anion for these two ILs. In addition, we used a combination of area normalisation and subtraction of XP spectra to produce what are effectively XP spectra for individual ions; this was achieved for seven cations and 14 anions.

LiMn 2O 4 is a promising candidate for a cathode material in lithium-ion batteries because of its ability to intercalate lithium ions reversibly through its three-dimensional manganese oxide network. One of the promising techniques for depositing LiMn 2O 4 thin-film cathodes is atomic layer deposition (ALD). Because of its unparalleled film thickness control and film conformality, ALD helps to fulfill the industry demands for smaller devices, nanostructured electrodes, and all-solid-state batteries. In this work, the intercalation mechanism of Li + ions into an ALD-grown β-MnO 2 thin film was studied. Samples were prepared by pulsing LiO tBu and H 2O for different cycle numbers onto about 100 nm thick MnO 2 films at 225 °C and characterized with X-ray absorption spectroscopy, X-ray diffraction, X-ray reflectivity, time-of-flight elastic recoil detection analysis, and residual stress measurements. It is proposed that for tBu/H 2O, the Li + ions penetrate only to the surface region of the β-MnO 2 film, and the samples form a mixture of β-MnO 2 and a lithium-deficient nonstoichiometric spinel phase Li xMn 2O 4 (0 < x < 0.5). When the lithium concentration exceeds x ≈ 0.5 in Li xMn 2O 4 (corresponding to 100 cycles of LiO tBu/H 2O), the crystalline phase of manganese oxide changes from the tetragonal pyrolusite to the cubic spinel, which enables the Li + ions to migrate throughout the whole film. Annealing in N 2 at 600 °C after the lithium incorporation seemed to convert the films completely to the pure cubic spinel LiMn 2O 4.

The exceptional thermal and chemical stability of the UiO-66, -67 and -68 classes of isostructural MOFs [J. Am. Chem. Soc., 2008, 130, 13850] makes them ideal materials for functionalization purposes aimed at introducing active centres for potential application in heterogeneous catalysis. We previously demonstrated that a small fraction (up to 10%) of the linkers in the UiO-67 MOF can be replaced by bipyridine-dicarboxylate (bpydc) moieties exhibiting metal-chelating ability and enabling the grafting of Pt(ii) and Pt(iv) ions in the MOF framework [Chem. Mater., 2015, 27, 1042] upon interaction with PtCl2 or PtCl4 precursors. Herein we extend this functionalization approach in two directions. First, we show that by controlling the activation of the UiO-67-Pt we can move from a material hosting isolated Pt(ii) sites anchored to the MOF framework with Pt(ii) exhibiting two coordination vacancies (potentially interesting for C–H bond activation) to the formation of very small Pt nanoparticles hosted inside the MOF cavities (potentially interesting for hydrogenation reactions). The second direction consists of the extension of the approach to the insertion of Cu(ii), obtained via interaction with CuCl2, and exhibiting interesting redox properties. All materials have been characterized by in situ X-ray absorption spectroscopy at the Pt L3- and Cu K-edges.

Near-infrared emitting persistent phosphors have promising applications in the field of in vivo medical imaging. In this paper, we prepared the persistent phosphor LiGa5O8:Cr3+ (LGO:Cr) which exhibits emission in the tissue transparency window and shows afterglow for multiple hours after excitation. Addition of Si or Ge improves the persistent luminescence. X-ray diffraction and electron microscopy, coupled with elemental analysis, revealed that there is a maximum amount of Si or Ge that can be incorporated in the host. Via X-ray absorption spectroscopy and electron paramagnetic resonance experiments, we studied the local environment of chromium in the LGO spinel host. The presence of both Cr3+ and Cr4+ on octahedral sites in LGO was confirmed. Electron paramagnetic resonance showed that Cr3+ resides in a rhombically distorted octahedral lattice site and that the Cr3+ local environment is sensitive to variation in point defects in the surrounding.

We explore the high spectral resolution X-ray data towards the quasar 3C273 to search for signals of hot ($\sim10^{6-7}$ K) X-ray-absorbing gas co-located with two established intergalactic FUV OVI absorbers. We analyze the soft X-ray band grating data of all XMM-Newton and Chandra instruments to search for the hot phase absorption lines at the FUV predicted redshifts. The viability of potential line detections is examined by adopting the constraints of a physically justified absorption model. The WHIM hypothesis is investigated with a complementary 3D galaxy distribution analysis, and by comparison of the measurement results to the WHIM properties in the EAGLE cosmological, hydrodynamical simulation. At FUV redshift z=0.09017, we measured signals of two hot ion species, OVIII and NeIX, with a $3.9\sigma$ combined significance level. Considering the line features in all instruments collectively and assuming collisional equilibrium for absorbing gas, we were able to constrain the temperature ($kT=0.26\pm0.03$ keV) and the column density ($N_H\times{Z_\odot/Z}=1.3_{-0.5}^{+0.6}\times10^{19}$ cm$^{-2}$) of the absorber. Thermal analysis indicates that FUV and X-ray absorption relate to different phases, with estimated temperatures $T_{FUV}\approx3\times10^5$ and $T_{X-ray}\approx3\times10^6$ K, which match the EAGLE predictions for WHIM at the FUV/X-ray measured $N_{ion}$-ranges. We detected a large scale galactic filament crossing the sightline at the redshift of the absorption, linking the absorption to this structure. This study provides insights into co-existing warm and hot gas within a WHIM filament and estimates the ratio of the hot and warm phases. Because the hot phase is thermally distinct from the OVI gas, the estimated baryon content of the absorber is increased, conveying the promise of X-ray follow-up studies of FUV detected WHIM in refining the picture of the missing baryons., Comment: 17 pages, 10 figures, accepted for publication in A&A

The analysis of iron, manganese and antimony in silicate glass is of great interest in chemistry, materials science, earth sciences and archaeological sciences. Yet, conclusions from different fields appear to be contradictory and many questions about redox reactions in glass remain. The purpose of this study is thus to discuss whether and how these multivalent elements interact in glass. Soda-lime silicate melts containing iron along with manganese and/or antimony have been analysed at different high temperatures under argon atmosphere. Using in-situ XANES at the Fe K-edge, redox thermodynamics, kinetics and diffusivities have been assessed for the different compositions. The data obtained show that antimony is more efficient at oxidising iron compared to manganese at all temperatures. The oxidising power trend would thus be Sb > Sb + Mn > Mn. Furthermore, hypotheses on the formation of Fe-Mn complexes are also reported in glasses with stoichiometric proportions of iron and manganese. Based on the determination of redox diffusivities, it appears that presence of other multivalent elements does not significantly affect the iron redox mechanisms and that diffusivity is essentially controlled by the mobility of calcium.

International audience; Carlo Lamberti opened discussion of the introductory lecture by Bruce Gates: As you have shown, EXAFS plays a crucial role in determining the structure and the nuclearity of nanoparticles (NPs). For each shell, the accuracy of this determination depends on the error bar associated to the coordination number, that strongly correlates with the corresponding Debye–Waller (DW) parameter. This becomes even more important when in situ operando experiments are performed at reaction temperature. Based on your experience, what suggestions can you give to reduce this correlation and increase the potentiality of the technique? Do you believe it is possible to fix or to determine, in a reliable way, DW parameters from independent experimental or computational works? Do you believe that in temperature-dependent experiments it is reliable to adopt th eDebye or the Einstein model to parametrize the evolution of DW parameters?

Transmission electron microscopy (TEM) is commonly used as an ex-situ technique to determine structural changes by comparing images of catalyst particles before and after a reaction. This requires the use of an alcoholic solvent to disperse the particles on a grid. In this work, we will show that Pd catalysts can be transformed during the procedure, by using EXAFS to determine the structure of Pd catalysts in different environments (as dry or wet samples). Supported palladium nanoparticles exposed to aqueous ethanolic solution (50% w/v) are transformed to a common, reduced, and hydrogen-contaminated state, irrespective of their initial habit or support. Catalysts comprised of nanosize PdO are reduced at ca. 350 K, whereas samples comprised of very small (ca. ≤ 10 atoms) Pd particles react with the solvent at just above room temperature and agglomerating with considerable loss of dispersion. As such any potential benefits to catalysis sought through the synthesis of very highly dispersed metallic Pd supported upon a range of inorganic dispersants will be rapidly erased through the action of such solvents.

The high resolution near edge X-ray absorption fine structure spectrum of nitrogen displays the vibrational structure of the core-excited states. This makes nitrogen well suited for assessing the accuracy of different electronic structure methods for core excitations. We report high resolution experimental measurements performed at the SOLEIL synchrotron facility. These are compared with theoretical spectra calculated using coupled cluster theory and algebraic diagrammatic construction theory. The coupled cluster singles and doubles with perturbative triples model known as CC3 is shown to accurately reproduce the experimental excitation energies as well as the spacing of the vibrational transitions. The computational results are also shown to be systematically improved within the coupled cluster hierarchy, with the coupled cluster singles, doubles, triples, and quadruples method faithfully reproducing the experimental vibrational structure. This is the authors’ accepted and refereed manuscript to the article. This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in Journal of Chemical Physics and may be found at https://doi.org/10.1063/1.5011148

International audience; We report on our investigation of the electronic structure of Ti2O3 using (hard) x-ray photoelectron and soft x-ray absorption spectroscopy. From the distinct satellite structures in the spectra, we have been able to establish unambiguously that the Ti-Ti c-axis dimer in the corundum crystal structure is electronically present and forms an a(1g)a(1g) molecular singlet in the low-temperature insulating phase. Upon heating, we observe a considerable spectral weight transfer to lower energies with orbital reconstruction. The insulator-metal transition may be viewed as a transition from a solid of isolated Ti-Ti molecules into a solid of electronically partially broken dimers, where the Ti ions acquire additional hopping in the a-b plane via the e(g)(pi) channel, the opening of which requires consideration of the multiplet structure of the on-site Coulomb interaction.

The electronic properties of three vanadium phthalocyaninato (Pc) based complexes (PcV, PcVO, and PcVI; I-III, respectively) were theoretically investigated and corresponding VL2,3-edge XAS spectra modeled. Ground state (GS) DFT outcomes indicated that II is more stable than III by 141 kcal/mol; moreover, the Ziegler transition state method allowed us to estimate the PcV-X bond dissociation energy and to quantify ?/? contributions to the V-X interaction. As such, the Nalewajski-Mrozek V-X and V-N bond multiplicity indexes (V-O/V-I = 2.48/1.22; V-N = 0.64, 0.51, and 0.58 in I-III, respectively) state that the V-X bond strength and nature affect the V-N interaction. The coordination of X to V in the I -> II/I -> III reactions implies the transfer of two/one electrons from I to X. In both cases, the oxidation involves only the V ion; moreover, V 3d based orbitals from which electrons are transferred were identified. Literature I/IIL2,3-edge XAS data were modeled by exploiting the DFT/ROCIS method. The same protocol was adopted to predict IIIL2,3-edge XAS spectra. Theoretical results indicated that, along the whole series, spectral features lying at the lowest excitation energies (EEs) are mostly generated by states having the same GS spin multiplicity and involve 2pV -> SOMO (single occupied molecular orbital) single electronic excitations. XAS features at higher EEs include only states with the same GS spin multiplicity in I, while states with both ?S = 0 and ?S = +1 (S = total spin quantum number) are present in II and III with significant, in some cases prevailing, contributions from metal to ligand charge transfer (MLCT) excitations. Beyond the role played by MLCT transitions in determining XAS patterns, it is noteworthy that they involve only Pc-based empty orbitals with no participation of the X-based virtual levels.

Once penetrated into the lungs of exposed people, asbestos induces an in vivo biomineralisation process that leads to the formation of a ferruginous coating embedding the fibres. The ensemble of the fibre and the coating is referred to as asbestos body and is believed to be responsible for the high toxicological outcome of asbestos. Lung tissue of two individuals subjected to prolonged occupational exposure to crocidolite asbestos was investigated using synchrotron radiation micro-probe tools. The distribution of K and of elements heavier than Fe (Zn, Cu, As, and Ba) in the asbestos bodies was observed for the first time. Elemental quantification, also reported for the first time, confirmed that the coating is highly enriched in Fe (~20% w/w), and x-ray absorption spectroscopy indicated that Fe is in the 3+ oxidation state and that it is present in the form of ferritin or hemosiderin. Comparison of the results obtained studying the asbestos bodies upon removing the biological tissue by chemical digestion and those embedded in histological sections, allowed unambiguously distinguishing the composition of the asbestos bodies, and understanding to what extent the digestion procedure altered their chemical composition. A speculative model is proposed to explain the observed distribution of Fe.

In this review we provide an overview of the potential of synchrotron radiation techniques to understand the structural and electronic properties of coordination compounds. Besides the largely employed multi-wavelength anomalous dispersion (MAD) and X-ray absorption spectroscopy (XAS), in both near (XANES) and post (EXAFS) edge regions, we also discuss the contribution arising from more specialized techniques that have become more widely used in the last years, such as the total scattering approach in the XRPD data analysis and X-ray emission spectroscopy (XES). Comparison with the commonly used laboratory techniques (XRD, UV–vis, luminescence, NMR, EPR) is used to underline the added value of synchrotron radiation techniques when applied to already well characterized samples. The fundamental role of DFT calculations in interpreting both diffraction and spectroscopic data to understand structural and electronic properties of coordination complexes is highlighted. A perspective summary is reported at the end of the manuscript.

Ferrihydrite (Fh) is an yet enigmatic nano Fe(III)-oxide material, omnipresent in nature that can bind ions in large quantities, regulating bioavailability and ion mobility. Although extensively studied, to date no proper view exists on the surface structure and composition, while it is of vital importance to our understanding of ion complexation in terrestrial and aquatic systems. Here, the surface structure of Fh is elucidated in relation to that of the mineral core, showing a unique surface composition differing from the mineral core. The mineral core is basically defect-free for all Fh particles. Key for understanding Fh is the very large contribution of the surface as an “inter-phase”. The surface of Fh is depleted by two specific types of polyhedra (Fe2,Fe3). Surface depletion (SD) explains the observed particle size dependency of the (a) Pair Distribution Function (PDF) derived from High Energy X-ray total Scattering (HEXS), (b) thermogravimetric water content, and (c) mass density. It also explains the isotopic 57Fe exchange ratio. Due to surface groups, two-line Fh particles are water rich but its mineral core is hydrogen poor. The SD model elucidates the surface structure of crystal faces of idealized Fh such as the 1 −1 0 and 1 −1 1 type of faces that may strongly contribute (e.g. ∼75 ± 10%) to the total surface area. These faces are terminated by protruding Fe1 octahedra, creating the singly-coordinated FeOH(H) groups at the Fh surface. Alternating rows of Fe1 octahedra with singly-coordinated surface groups enable the formation of either double corner (2C) or edge (1E) surface complexes. For Fh, the site densities derived are much higher than for goethite. In combination with the high surface area, it makes Fh to an extremely reactive natural phase.

Journal of materials chemistry / A 5(31), 16296 - 16306 (2017). doi:10.1039/C7TA02316B special issue: "Green Materials and Surfaces", Herein, a cost-effective and tailored synthesis route for the preparation of cubic ZrO$_2$ nanocrystals with high dispersibility (up to 45% by weight in H$_2$O) is reported. The procedure is straightforward and produces uniform 2–3 nm particles of a high yield of up to 98% when applying microwave dielectric heating as a “green” method. Furthermore, it can be applied to a wide range of batch sizes (from 0.5 to 20 g ZrO$_2$), which makes it interesting for industrial applications, and also lends itself to the preparation of yttria-stabilized ZrO$_2$ nanocrystals with varying doping levels. Overall, the paper aims at unravelling all relevant reaction steps by means of nuclear magnetic resonance and gas chromatography-mass spectrometry. Two innovative synthesis routes are presented, which have not been considered in previous studies. Both the microstructure and chemical composition of the nanoparticles were analyzed via electron microscopy, X-ray diffraction and dynamic light scattering as well as Raman, X-ray absorption and X-ray photoelectron spectroscopy. Besides, it is demonstrated that alcoholic ZrO$_2$ dispersions are highly suited for the preparation of nanoscale materials with different morphologies, including fibers as well as ordered mesoporous and macroporous thin films and powders. Collectively, this work provides a blueprint for the fabrication of high-quality nanoparticles and structured materials thereof and is likely to trigger further research in the field of solution-processed metal oxides., Published by RSC, London [u.a.]

The small pore Cu-CHA zeolite is attracting increasing attention as a versatile platform to design novel single-site catalysts for deNOx applications and for the direct conversion of methane to methanol. Understanding at the atomic scale how the catalyst composition influences the Cu-species formed during thermal activation is a key step to unveil the relevant composition–activity relationships. Herein, we explore by in situ XAS the impact of Cu-CHA catalyst composition on temperature-dependent Cu-speciation and reducibility. Advanced multivariate analysis of in situ XANES in combination with DFT-assisted simulation of XANES spectra and multi-component EXAFS fits as well as in situ FTIR spectroscopy of adsorbed N2 allow us to obtain unprecedented quantitative structural information on the complex dynamics during the speciation of Cu-sites inside the framework of the CHA zeolite.

We report the development of sol-gel derived TiO2 thin films with adjustable and defined properties suitable for memristive cell fabrication. Memristive cells were developed by the sol-gel deposition of titania onto SiO2/Ti/Pt engineered electrodes via spin coating, followed by diverse curing and annealing procedures. The influence of the processing conditions and the sol's chemical composition on the film properties, and therefore on the memristive response, was studied by micro-Raman and transmission spectroscopies, profilometry, ellipsometry, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and X-ray absorption and diffraction spectroscopies (XAS and XRD). A memristive response was acquired from a number of these cells, revealing a dependence of the electrical behavior on minor changes in the TiO2 structure, electroforming parameters, and architecture. Thus, these properties provide a handle for fine-tuning electrical performance.

Amorphous transition metal oxides [aTMOs], have emerged as innovative functional materials for wide-ranging electronic, optical and energy-related applications. However, no systematic and broadly applicable method exists to assess their atomic-scale correlations, and since the optical and electronic processes are local structure-dependent, still there are not well-stablished mechanisms that suitably explain the physical properties of aTMOs. This thesis presents experimental and theoretical studies of the atomic short-range order, optical and electronic properties, and state-defects induced by Li+-ion-intercalation and oxygen-vacancies in amorphous titanium aTiO2 and tungsten aWO3 thin-film oxides. Those properties play a key role for application in high energy-density Li+-ion batteries and in switchable dynamical modulation of solar-irradiation transmittance for energy efficient "smart windows", where the disorder-dependent Li+-ion-intercalation and oxygen-vacancy-induced defect-states influence charge-carrier transfer mechanisms. After introducing the scope of this thesis, the fundamental theoretical concepts describing the experimental findings on amorphous solids are reviewed. Thereafter, a comprehensive analysis on the optical absorption phenomena experimentally observed in oxygen-deficient and Li+-ion-intercalated aLixTiO2−y and aLixWO3−y thin-films and a discussion on the electrochromic properties are presented. The optical absorption is described in the framework of the small polaron absorption model. Finally, a state-of-the-art systematic procedure involving theory and experiment in a self-consistent computational framework is implemented to unveil the atomic-scale structure of aTiO2 and aWO3, and its role for the electronic properties. The procedure is based in Reverse Monte Carlo [RMC] and Finite Difference Method [FDM] simulations of X-ray-Absorption spectra to construct a disordered theoretical model having the same bonding and coordination distribution as the experimental system. Ab-initio molecular dynamics simulations and density functional theory are then used to assess defect-states induced by Li+-ion-intercalation and oxygen-vacancies in aTiO2 and aWO3 oxides. The schemes introduced in this study offer a consistent route to experimentally and theoretically assess the role of the atomic-scale structure on the optical and electronic properties of aTiO2 and aWO3 and could be extended to the study of other aTMOs. The final results provide crucial insight towards the understanding of optical and electronic mechanisms where disorder-dependent ion-intercalation and oxygen-vacancy-induced localized defect-states influence charge transfer mechanisms of crucial importance for wide ranging optical and energy-related application of aTiO2 and aWO3 oxides.

The occupied and unoccupied electronic structures of three high spin TM(acac) 3 (TM = Cr, Mn, and Fe) complexes (I, II, and III, respectively) were studied by revisiting their literature vapour- phase He(I) and, when available, He(II) photoemission (PE) spectra and by means of original near- edge X- ray absorption fine structure (NEXAFS) spectroscopic data recorded at the OK-edge (OK-edge) and TM (L2,3)- edges (TML2,3- edges). The assignments of the vapour-phase He(I)/He(II) PE spectra were guided by the results of spin- unrestricted non- relativistic Slater transition state calculations, while the OK- edge and TM(L2,3)edge spectroscopic pieces of evidence were analysed by exploiting the results of spin-unrestricted scalar-relativistic time-dependent density functional theory (DFT) and DFT/ROCIS calculations, respectively. Although the actual symmetry (D-3, in the absence of any Jahn-Teller distortion) of the title molecules allowed an extensive mixing between TM t(2g)- like and eg- like atomic orbitals, the use of the Nalewajski- Mrozek TM-O bond multiplicity index combined with a thorough analysis of the ground state (GS) outcomes allowed the assessment of the TM-O bond weakening associated with the progressive TM 3d- based e(g)- like orbital filling. The experimental information provided by K-O- edge spectra was rather poor; nevertheless, the combined use of symmetry, orbitals and spectra allowed us (i) to rationalise minor differences characterizing spectral features along the series, (ii) to quantify the contribution provided by the ligand-to-metal-charge-transfer (LMCT) excitations to the different spectral features, and (iii) to recognize the t2g-/eg- like nature of the TM 3d- based orbitals involved in LMCT transitions. As far as the TML2,3- edge spectra and the DFT/ROCIS results were concerned, the lowest lying L-I, II(3) spectral features included states having either the GS spin multiplicity (S(I) = 3/2, S(II) = 2) or, at higher excitation energies (EEs), states with Delta S = +/- 1. In contrast to that, only states with Delta S = 0, -1 significantly contributed to the IIIL3 spectral pattern. Along the whole series, the L-3 higher EE side was systematically characterized by states involving (TM)2p pi(4) MLCT excitations; as such, coupled- single excitations with DS = 0 were involved in I and II, while single MLCT (TM)2p pi(4) transitions with Delta S = -1 were involved in III.