Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides.

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure. Increasing the Fe precursor oxidation state gives decreased Fe-ion occupation and increased Mo-ion occupation of tetrahedral sites, as revealed by the extended X-ray absorption fine structure. The stabilization of Mo within tetrahedral sites appears to be unexpected, considering the octahedral preferred coordination number of Mo(VI). The analysis of the atomic structure of the sample prepared with Fe(III) indicates a local ordering of vacancies and that the occupation of tetrahedral sites by Mo induces a contraction of the interatomic distances within the polyhedra as compared to Fe atoms. Moreover, the occupancy of Mo into the thermodynamic site preference of a Mo dopant in Fe2O3 assessed by density functional theory calculations points to a stronger preference for Mo substitution at octahedral sites. Hence, we suggest that the synthetized compound is thermodynamically metastable, that is, kinetically trapped. Such a state is suggested to be a consequence of the tetrahedral site occupation by Mo ions. The population of these sites, known to be reactive sites enabling particle growth, is concomitant with the stabilization of very small particles. We confirmed our hypothesis by using a blank experiment without Mo ions, further supporting the impact of tetrahedral Mo ions on the growth of iron oxide nanoparticles. Our findings provide new insights into the relationships between the Fe-chemistry of the crystallizing solution and the structural features of the as-grown Mo-substituted Fe-oxide materials.

The rise of X-ray spectroscopies for unveiling the functional mechanisms in batteries.

Synchrotron-based techniques have been key tools in the discovery, understanding, and development of battery materials. In this review, some of the most suitable X-ray spectroscopy related techniques employed for addressing diverse scientific cases connected to battery science are highlighted. Furthermore, current shortcomings, intrinsic limitations, and ongoing challenges of individual techniques are pointed out, providing an outlook of future trends that are relevant to the battery research community. In particular, the ongoing development of next generation synchrotrons, machine learning algorithms for data analysis and combined theoretical/experimental approaches will enhance the already powerful assets of these advanced spectroscopic methods.

Quantum-Chemical Study of the FeNCN Conversion-Reaction Mechanism in Lithium- and Sodium-Ion Batteries.

We report a computational study on 3d transition-metal (Cr, Mn, Fe, and Co) carbodiimides in Li- and Na-ion batteries. The obtained cell voltages semi-quantitatively fit the experiments, highlighting the practicality of PBE+U as an approach for modeling the conversion-reaction mechanism of the FeNCN archetype with lithium and sodium. Also, the calculated voltage profiles agree satisfactorily with experiment both for full (Li-ion battery) and partial (Na-ion battery) discharge, even though experimental atomistic knowledge is missing up to now. Moreover, we rationalize the structural preference of intermediate ternaries and their characteristic lowering in the voltage profile using chemical-bonding and Mulliken-charge analysis. The formation of such ternary intermediates for the lithiation of FeNCN and the contribution of at least one ternary intermediate is also confirmed experimentally. This theoretical approach, aided by experimental findings, supports the atomistic exploration of electrode materials governed by conversion reactions.

Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials.

While platinum has hitherto been the element of choice for catalysing oxygen electroreduction in acidic polymer fuel cells, tremendous progress has been reported for pyrolysed Fe-N-C materials. However, the structure of their active sites has remained elusive, delaying further advance. Here, we synthesized Fe-N-C materials quasi-free of crystallographic iron structures after argon or ammonia pyrolysis. These materials exhibit nearly identical Mössbauer spectra and identical X-ray absorption near-edge spectroscopy (XANES) spectra, revealing the same Fe-centred moieties. However, the much higher activity and basicity of NH3-pyrolysed Fe-N-C materials demonstrates that the turnover frequency of Fe-centred moieties depends on the physico-chemical properties of the support. Following a thorough XANES analysis, the detailed structures of two FeN4 porphyrinic architectures with different O2 adsorption modes were then identified. These porphyrinic moieties are not easily integrated in graphene sheets, in contrast with Fe-centred moieties assumed hitherto for pyrolysed Fe-N-C materials. These new insights open the path to bottom-up synthesis approaches and studies on site-support interactions.

Characterization of Phosphate Species on Hydrated Anatase TiO2 Surfaces.

The adsorption/interaction of KH2PO4 with solvated (100) and (101) TiO2 anatase surfaces is investigated using periodic DFT calculations in combination with GIPAW NMR calculations and experimental IR and solid state (17)O, and (31)P NMR spectroscopies. A complete and realistic model has been used to simulate the solvent by individual water molecules. The most stable adsorption configurations are characterized theoretically at the atomic scale, and experimentally supported by NMR and IR spectroscopies. It is shown that H2PO4(-) chemisorbs on the (100) and (101) anatase surfaces, preferentially via a bidentate geometry. Dimer (H3P2O7(-)) and trimer (H4P3O10(-)) adsorption models are confronted with monomer adsorption models, in order to rationalize their occurrence.

Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties.

We report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on (57)Fe Mössbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe-NCN into Li/Na-NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not require heavy treatments (such as nanoscale tailoring, sophisticated textures, or coating) to obtain long cycle life with current density as high as 9 A g(-1) for hundreds of charge-discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides M(x)(NCN)y with M=Mn, Cr, Zn can cycle successfully versus lithium and sodium. Their electrochemical activity and performance open the way to the design of a novel family of anode materials.

The Quest for Polysulfides in Lithium-Sulfur Battery Electrolytes: An Operando Confocal Raman Spectroscopy Study.

Confocal Raman spectra of a lithium-sulfur battery electrolyte are recorded operando in a depth-of-discharge resolved manner for an electrochemical cell with a realistic electrolyte/sulfur loading ratio. The evolution of various possible polysulfides is unambiguously identified by combining Raman spectroscopy data with DFT simulations.

X-ray absorption near-edge structure and nuclear magnetic resonance study of the lithium-sulfur battery and its components.

Understanding the mechanism(s) of polysulfide formation and knowledge about the interactions of sulfur and polysulfides with a host matrix and electrolyte are essential for the development of long-cycle-life lithium-sulfur (Li-S) batteries. To achieve this goal, new analytical tools need to be developed. Herein, sulfur K-edge X-ray absorption near-edge structure (XANES) and (6,7) Li magic-angle spinning (MAS) NMR studies on a Li-S battery and its sulfur components are reported. The characterization of different stoichiometric mixtures of sulfur and lithium compounds (polysulfides), synthesized through a chemical route with all-sulfur-based components in the Li-S battery (sulfur and electrolyte), enables the understanding of changes in the batteries measured in postmortem mode and in operando mode. A detailed XANES analysis is performed on different battery components (cathode composite and separator). The relative amounts of each sulfur compound in the cathode and separator are determined precisely, according to the linear combination fit of the XANES spectra, by using reference compounds. Complementary information about the lithium species within the cathode are obtained by using (7) Li MAS NMR spectroscopy. The setup for the in operando XANES measurements can be viewed as a valuable analytical tool that can aid the understanding of the sulfur environment in Li-S batteries.

Understanding Na+ Diffusion, Physicochemical Behavior, and Electrochemical Performance of a Gel Polymer Electrolyte.

Gel polymer electrolytes (GPEs) represent a credible alternative to organic liquid electrolytes (LEs) for safer sodium metal batteries. As a compromise between solid polymer electrolytes and LEs, GPEs ensure a good ionic conductivity, improve the electrolyte/electrode interface, and prevent solvent leaks. Herein, a GPE based on acrylate-bifunctionalized polyethylene glycol chains mixed with an ether solvent (TEGDME) and a polyethylene glycol diacrylate (PEG600DA) in a 50/50 wt % ratio was prepared by ultraviolet photopolymerization. Sodium bis(fluorosulfonyl)imide salt (NaFSI) was added at different concentrations to study its interactions with the solvent and/or the cross-linked polymer. Infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and swelling ratio characterizations were combined to determine the physicochemical properties of the GPE. Complementary characterizations including electrochemical impedance spectroscopy, chronopotentiometry, and cyclic voltammetry allowed correlating the physicochemical properties of the GPE to its electrochemical performance. Then, improvements were obtained by careful combination of its components. The cross-linking agent allowed us to obtain a polymer matrix that traps the organic solvent and prevents leakage. Such a solvent inclusion reduces the rigidity of the membrane and lowers its viscosity, offering a room temperature ionic conductivity of 4.8 × 10-4 Ω-1 cm-1. The control of polymer's tortuosity leads to a stable cycling vs sodium metal over several hundred hours without increase of the polarization. Finally, optimization of the salt loading plays a major role in electrostatic cross-linking, leading to an improvement of the mechanical properties of the GPE without reducing its conductivity.

Lithium and cobalt extraction from LiCoO2 assisted by p(VBPDA-co-FDA) copolymers in supercritical CO2.

Supercritical CO2 (scCO2) extraction assisted by complexing copolymers is a promising process to recover valuable metals from lithium-ion batteries (LIBs). CO2, in addition to being non-toxic, abundant and non-flammable, allows an easy separation of metal-complexes from the extraction medium by depressurization, limiting the wastewater production. In this study, CO2-philic gradient copolymers bearing phosphonic diacid complexing groups (poly(vinylbenzylphosphonic diacid-co-1,1,2,2-tetrahydroperfluorodecylacrylate), p(VBPDA-co-FDA)) were synthesized for the extraction of lithium and cobalt from LiCoO2 cathode material. Notably, the copolymer was able to play the triple role of leaching agent, complexing agent and surfactant. The proof of concept for leaching, complexation and extraction was achieved, using two different extraction systems. A first extraction system used aqueous hydrogen peroxide as reducing agent while it was replaced by ethanol in the second extraction system. The scCO2 extraction conditions such as extraction time, temperature, functional copolymer concentration, and the presence of additives were optimized to improve the metals extraction from LiCoO2 cathode material, leading to an extraction efficiency of Li and Co up to ca. 75 % at 60 °C and 250 bar.

Sophorolipids-functionalized iron oxide nanoparticles.

Functional iron oxide nanoparticles (NP) have been synthesized in a one and a two-step method using a natural functional glycolipid belonging to the family of sophorolipids (SL). These compounds, whose open acidic form is highly suitable for nanoparticle stabilization, are readily obtained by a fermentation process of the yeast Candida bombicola (polymorph Starmerella bombicola) in large amounts. The final carbohydrate coated iron oxide nanoparticles represent interesting potentially biocompatible materials for biomedical applications. According to the synthesis strategy, magnetic properties can eventually be tuned, thus putting in evidence the direct effect of the glycolipid on the final material's structure (maghemite and ferrihydrite have been obtained here). A combination of FT-IR, Dynamic Light Scattering (DLS) and UV-Vis experiments shows that SL complex the nanoparticle surface via their accessible COOH group thus forming stable colloids, whose hydrodynamic diameter mostly varies between 10 nm and 30 nm, both in water and in KCl-containing (0.01 M and 2 M) solutions. The materials can stand multiple filtration steps (up to 10) at different extents, where the largest recorded average aggregate size is 100 nm. In general, materials synthesized at T = 80 °C display better stability and smaller size distribution than those obtained at room temperature.

A comparative study of the catalysis of peptide bond formation by oxide surfaces.

It is well-known that amino acids deposited on some inorganic oxides undergo peptidic condensation. It is seldom realised however that a large diversity of behaviours can be observed in such systems. Here we use the apparently simple case of glycine-non-porous silica as a reference system, in which glycine (Gly) dimerisation to diketopiperazine (DKP) is easy to evidence, especially when using TG in combination with NMR. We then proceed to compare it with other AA deposited on the same support on the one hand, with Gly deposited on other mineral surfaces on the other hand. In a final section, we provide more detailed mechanistic information on the glycine condensation process on silica, including kinetic data and a (13)C solid-state NMR follow up of the species at various stages of thermal condensation. The best mechanism to rationalise these data involves a crucial step of isomerisation from zwitterion to neutral glycine, and the participation of several distinct types of surface sites probably consisting of silanol ensembles.

Single-Atomic Dispersion of Fe and Co Supported on Reduced Graphene Oxide for High-Performance Lithium-Sulfur Batteries.

High theoretical energy density and low cost make lithium-sulfur (LSB) batteries a promising system for next-generation energy storage. LSB performance largely depends on efficient reversible conversion of elemental sulfur to Li2S. Here, well-designed sulfur host materials including Fe or Co single atoms embedded on N-doped reduced graphene oxide (MNC/G with M = Fe or Co) are proposed to tackle the LSB challenges and enhance the electrochemical performance. Using a combination of Mössbauer spectroscopy and high-resolution scanning electron microscopy, the atomic dispersion of Co and Fe was revealed up to relatively high mass loadings. After optimization of the electrolyte/sulfur (E/S) ratio, FeNC/G shows the most promising cycle performance combining a constant high discharge capacity at low E/S values with the lowest polarization. In particular, the material FeNC/G@S with a high sulfur loading (9.4 mg cm-2) delivers a high area capacity of 7.7 mAh cm-2 under lean electrolyte conditions (6 mL g-1).

Better cycling performances of bulk Sb in Na-ion batteries compared to Li-ion systems: an unexpected electrochemical mechanism.

Pure micrometric antimony can be successfully used as negative electrode material in Na-ion batteries, sustaining a capacity close to 600 mAh g(-1) at a high rate with a Coulombic efficiency of 99 over 160 cycles, an extremely high capacity compared to any other compound tested against both Li and Na. The reaction mechanism with Na does not simply go through the alloying mechanism observed for Li where the intermediate species are those expected from the phase diagram. In the case of Na, the intermediate phases are mostly amorphous and could not be precisely identified. Surprisingly, we evidenced that a competition takes place at the end of the discharge of the Sb/Na cell between the formation of the hexagonal and the cubic polymorphs of Na(3)Sb, the last being described in the literature as unstable at atmospheric pressure and only synthesized under high pressure (1-9 GPa). In addition, fluoroethylene carbonate added to the electrolyte combined with an appropriate electrode formulation based on carboxymethyl cellulose, carbon black, and vapor ground carbon fibers seems to be determinant in the excellent performances of this material.

Mechanism of RuO2 crystallization in borosilicate glass: an original in situ ESEM approach.

Ruthenium, a fission product arising from the reprocessing of spent uranium oxide (UOX) fuel, crystallizes in the form of acicular RuO(2) particles in high-level waste containment glass matrices. These particles are responsible for significant modifications in the physicochemical behavior of the glass in the liquid state, and their formation mechanisms are a subject of investigation. The chemical reactions responsible for the crystallization of RuO(2) particles with acicular or polyhedral shape in simplified radioactive waste containment glass are described. In situ high-temperature environmental scanning electron microscopy (ESEM) is used to follow changes in morphology and composition of the ruthenium compounds formed by reactions at high temperature between a simplified RuO(2)-NaNO(3) precursor and a sodium borosilicate glass (SiO(2)-B(2)O(3)-Na(2)O). The key parameter in the formation of acicular or polyhedral RuO(2) crystals is the chemistry of the ruthenium compound under oxidized conditions (Ru(IV), Ru(V)). The precipitation of needle-shaped RuO(2) crystals in the melt might be associated with the formation of an intermediate Ru compound (Na(3)Ru(V)O(4)) before dissolution in the melt, allowing Ru concentration gradients. The formation of polyhedral crystals is the result of the direct incorporation of RuO(2) crystals in the melt followed by an Ostwald ripening mechanism.

Iron topochemistry and surface reactivity of amphibole asbestos: relations with in vitro toxicity.

Chemical reactivity of asbestos tremolite from Italy and USA localities and Union Internationale Contre le Cancer (UICC) crocidolite was studied in relation to Fe content, oxidation state, and structural coordination. Direct correlation between amount of Fe(2+) at the exposed M(1) and M(2) sites of the amphibole structure and fiber chemical reactivity was established. The in vitro toxicity of the same samples was investigated on human alveolar A549 cell line. Relationship between crystal-chemical features and cell toxicity is not straightforward. UICC crocidolite has Fe content and chemical reactivity largely higher than that of tremolite samples, but all show comparable in vitro toxic potential. Results obtained evidenced that Fe topochemistry is not a primary factor for induced cell toxicity, though it accounts for asbestos chemical reactivity (and possibly genotoxicity).

Importance of Halide Ions in the Stabilization of Hybrid Sn-Based Coatings for Lithium Electrodes.

The properties of hybrid Sn-based artificial solid electrolyte interphase (SEI) layers in protecting Li-metal electrodes toward surface instabilities were investigated via a combined experimental and theoretical approach. The performance of coating layers can be coherently explained based on the nature of the coating species. Notably, when starting from a chloride precursor, the hybrid coating layer is formed by an intimate mixture of Li7Sn2 and LiCl: the first ensures a high bulk ionic conductivity, while the second forms an external layer allowing a fast surface diffusion of Li+ to avoid dendrite growth, a low surface tension to guarantee the thermodynamic stability of the protective layer, and a negative underneath plating energy (UPE) to promote lithium plating at the interface between the Li metal and the coating layer. The synergy between the two components and, in particular, the crucial role of LiCl in the promotion of such an underneath plating mechanism are shown to be the key properties to improve the performance of artificial SEI layers.

Unveiling redox mechanism at the iron centers in the mechanochemically activated conversion of CO2 in the presence of olivine.

The transformation of olivine during the conversion of CO2 to light hydrocarbons activated by mechanochemical treatments at different impact frequencies was studied by a combination of several complementary characterization methods including X-ray diffraction, Raman and 57Fe Mössbauer spectroscopy. Several olivine samples were studied as a function of the milling time, indicating the gradual transformation of FeII-containing olivine into new FeIII-containing weathering products including iron oxides, magnesium iron carbonates and silicates. The results presented here complement those of a previous study on the weathering process of olivine promoted by mechanochemical activation, by demonstrating the role of the redox activity of the iron species during the activation process. These additional spectroscopic results allow us to thoroughly understand the complex weathering mechanism and to correlate it with the efficiency of the CO2 conversion and storage properties of mechanochemically activated olivine. Supplementary Information: The online version contains supplementary material available at 10.1007/s10853-022-06962-x.

Autocatalytic sonolysis of iron pentacarbonyl in room temperature ionic liquid [BuMeIm][Tf2N].

The autocatalytic sonochemical reaction of Fe(CO)(5) decomposition in [BuMeIm][Tf(2)N] provides iron nanoparticles in higher yields than in tetralin. Such a difference is explained by the higher decomposition of the intermediate Fe(3)(CO)(12) according to the two-sites model of the sonochemical reactions and the specific properties of the ionic liquid.

Ganyong Starch Derived Hard Carbon Anodes for Sodium Ion Batteries.

Hard carbons are one of the most promising carbon anode materials for sodium ion batteries (SIBs) due to the high specific capacity and excellent cycle properties. Among the precursors used to synthesize hard carbon, natural starches are of great interest due to their unique morphologies. In this paper, ganyong starch based hard carbons (GSHC) were prepared by direct carbonization at various temperatures (700-1100) °C. The obtained hard carbons exhibit high reversible capacities of sodium-ion batteries of about 239 mAh g-1 at current density of 0.1 C. after 100 cycles. The excellent cycle profiles are attributed to the unique morphology and defect carbon structures.