X-ray Absorption Spectroscopy Investigation Research Articles

Influence of support on Rh-Co bimetallic catalysts for ethylene hydroformylation

Bimetallic Rh- and Co-based catalysts are promising materials for the heterogenous ethylene hydroformylation reaction. Here, the influence of a mesoporous silica (SBA-15) support on Rh and Co bimetallic interactions was investigated through a comparison with silica gel and gamma-alumina supports. The bimetallic catalyst supported on mesoporous silica (RhCo3/SBA-15) showed the best C3 oxygenate yield among the three bimetallic catalysts. In-situ vibrational studies suggested moderate binding of the gem-dicarbonyl and Rh(CO)(C2H4) intermediates due to this bimetallic interaction that led to improved hydroformylation performance. Kinetic studies revealed a lower hydroformylation barrier for the bimetallic compared to a Rh monometallic catalyst, and in-situ X-ray absorption spectroscopy investigations showed clear Rh-Co alloy formation on RhCo3/SBA-15. The bimetallic enhancement effect from the interaction with the mesoporous silica support shown here can be further optimized to design olefin hydroformylation catalysts.

Catalytic Water Electrolysis by Co-Cu-W Mixed Metal Oxides: Insights from X-ray Absorption Spectroelectrochemistry.

Mixed metal oxides (MMOs) are a promising class of electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Despite their importance for sustainable energy schemes, our understanding of relevant reaction pathways, catalytically active sites, and synergistic effects is rather limited. Here, we applied synchrotron-based X-ray absorption spectroscopy (XAS) to explore the evolution of the amorphous Co-Cu-W MMO electrocatalyst, shown previously to be an efficient bifunctional OER and HER catalyst for water splitting. Ex situ XAS measurements provided structural environments and the oxidation state of the metals involved, revealing Co2+ (octahedral), Cu+/2+ (tetrahedral/square-planar), and W6+ (octahedral) centers. Operando XAS investigations, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), elucidated the dynamic structural transformations of Co, Cu, and W metal centers during the OER and HER. The experimental results indicate that Co3+ and Cu0 are the active catalytic sites involved in the OER and HER, respectively, while Cu2+ and W6+ play crucial roles as structure stabilizers, suggesting strong synergistic interactions within the Co-Cu-W MMO system. These results, combined with the Tafel slope analysis, revealed that the bottleneck intermediate during the OER is Co3+ hydroperoxide, whose formation is accompanied by changes in the Cu-O bond lengths, pointing to a possible synergistic effect between Co and Cu ions. Our study reveals important structural effects taking place during MMO-driven OER/HER electrocatalysis and provides essential experimental insights into the complex catalytic mechanism of emerging noble-metal-free MMO electrocatalysts for full water splitting.

An electrochemical flow cell for operando XPS and NEXAFS investigation of solid–liquid interfaces

Suitable reaction cells are critical for operando near ambient pressure (NAP) soft x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) studies. They enable tracking the chemical state and structural properties of catalytically active materials under realistic reaction conditions, and thus allow a better understanding of charge transfer at the liquid–solid interface, activation of reactant molecules, and surface intermediate species. In order to facilitate such studies, we have developed a top-side illuminated operando spectro-electrochemical flow cell for synchrotron-based NAP-XPS/-NEXAFS studies. Our modular design uses a non-metal (PEEK) body, and replaceable membranes which can be either of x-ray transparent silicon nitride (SiN x ) or of water permeable polymer membrane materials (e.g. NafionTM). The design allows rapid sample exchange and simultaneous measurements of total electron yield, Auger electron yield and fluorescence-yield. The developed system is highly modular and can be used in the laboratory or directly at the beamline for operando XPS/ x-ray absorption spectroscopy investigations of surfaces and interfaces. We present examples to demonstrate the capabilities of the flow cell. These include an operando NEXAFS study of the Cu-redox chemistry using a SiN x /Ti-Au/Cu working electrode assembly (WEA) and a NAP-XPS/-NEXAFS study of water adsorption on a NafionTM polymer membrane based WEA (NafionTM/C/IrO x catalyst). More importantly, the spectro-electrochemical flow cell is available for user community of B07 beamlines at Diamond Light Source.

X-ray absorption spectroscopy and theoretical investigations of the effect of extended ligands in potassium organic matter interaction.

Potassium (K) is an essential nutrient for plant growth, and despite its abundance in soil, most of the K is structurally bound in minerals, limiting its bioavailability and making this soil K reservoir largely inaccessible to plants. Microbial biochemical weathering has been shown to be a promising pathway to sustainably increase plant available K. However, the mechanisms underpinning microbial K uptake, transformation, storage, and sharing are poorly resolved. To better understand the controls on microbial K transformations, we performed K K-edge x-ray absorption near-edge structure (XANES) spectroscopy on K-organic salts, including acetate, citrate, nitrate, oxalate, and tartrate, which are frequently observed as low molecular weight organic acids secreted by soil microbes, as well as humic acid, which acts as a proxy for higher molecular weight organic acids. The organic salts display feature-rich K XANES spectra, each demonstrating numerous unique features spanning ∼13eV range across the absorption edge. In contrast, the spectra for humic acid have one broad, wide feature across the same energy range. We used a combination of time-dependent density functional theory and the Bethe-Salpeter equation based approach within the OCEAN code to simulate the experimental spectra for K-nitrate (KNO3) and K-citrate [K3(C6H5O7)·H2O] to identify the electronic transitions that give rise to some of the outlying and unique spectral features in the organic salts. KNO3 has both the lowest and highest lying energy features, and K3(C6H5O7)·H2O is produced by several soil microbes and is effective at mineral weathering. Our results analyze the K-organic salt bonding in detail to elucidate why the spectral shapes differ and indicate that the K K-edge XANES spectra are associated with the entire ligand despite similar first-shell bonding environments around the K center. The improved understanding of K bonding environments with organic ligands and their use for interpretation of the K-XANES spectra provides an important toolkit to understand how K is transformed by microbial processes and made bioavailable for plant uptake.

A novel electrochemical flow-cell for operando XAS investigations in X-ray opaque supports.

Improvement of electrochemical technologies is one of the most popular topics in the field of renewable energy. However, this process requires a deep understanding of the electrode-electrolyte interface behavior under operando conditions. X-ray absorption spectroscopy (XAS) is widely employed to characterize electrode materials, providing element-selective oxidation state and local structure. Several existing cells allow studies as close as possible to realistic operating conditions, but most of them rely on the deposition of the electrodes on conductive and X-ray transparent materials, from where the radiation impinges the sample. In this work, we present a new electrochemical flow-cell for operando XAS that can be used with X-ray opaque substrates, since the signal is effectively detected from the electrode surface, as the radiation passes through a thin layer of electrolyte (∼17 μm). The electrolyte can flow over the electrode, reducing bubble formation and avoiding strong reactant concentration gradients. We show that high-quality data can be obtained under operando conditions, thanks to the high efficiency of the cell from the hard X-ray regime down to ∼4 keV. We report as a case study the operando XAS investigation at the Fe and Ni K-edges on Ni-doped γ-Fe2O3 films, epitaxially grown on Pt substrates. The effect of the Ni content on the catalytic performances for the oxygen evolution reaction is discussed.

Operando x-Ray Absorption Spectroscopy Investigation of Secondary Metal Doping into Iron-Nitrogen-Carbon Catalysts for Oxygen Electroreduction

Oxygen reduction reaction (ORR) plays a key role in the development of fuel cell technology, and great efforts have been made to reduce the amount of platinum, required to speed up this sluggish reaction, or, even more desirable, to use efficient electrocatalysts based on earth-abundant metals. To date, numerous single-atom catalysts in the form of metal-doped carbon-nitrogen materials (MNC) have proved to be a promising alternative to ORR Pt-based materials. [1-3]In this study we employed advanced spectroscopic techniques, namely Mössbauer spectroscopy and operando X-ray absorption (XAS) spectroscopy, to understand the structural and electronic factors underlying an increase in the catalytic turn over frequency (TOF) of bimetallic FeSnNC and FeCoNC catalysts, relative to the parent FeNC materials. In particular, 57Fe Mössbauer spectroscopy identified a larger ratio of D1/D2 species in both bimetallic catalysts, supporting a larger ratio of Fe(III)-Nx/Fe(II)-Nx sites. The combination of extended X-ray absorption fine structure (EXAFS) modeling, and the analysis of operando X-ray absorption near-edge spectroscopy (XANES) spectra revealed a disordered carbon structure around FeNx active sites, and variations in the iron oxidation state that can be linked to the enhanced intrinsic catalytic reactivity (TOF). This talk is therefore intended to draw attention to the potential of the XAS technique, especially when applied to in-situ/operando studies in the field of electrocatalysis. References F. Luo, A. Roy, L. Silvioli, D.A. Cullen, A. Zitolo, M.T. Sougrati, I.C. Oguz, T. Mineva, D. Teschner, S. Wagner, J. Wen, F. Dionigi, U.I. Kramm, J. Rossmeisl, F. Jaouen and P. Strasser. P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction. Nature Materials 2020, 19, 1215-1223A. Zitolo, N. Ranjbar, T. Mineva, J. Li, Q. Jia, S. Stamatin, G.F. Harrington, S.M. Lyth, P. Krtil, S. Mukerjee, E. Fonda, F. Jaouen. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nature Communications 2017, 8(1), 957A. Zitolo, V. Goellner, V. Armel, M. T. Sougrati, T. Mineva, L. Stievano, E. Fonda, F. Jaouen. Identification of catalytic sites for oxygen reduction in iron and nitrogen doped graphene materials. Nature Materials 2015, 14, 937-942

Effect of Ag-Decorated BiVO4 on Photoelectrochemical Water Splitting: An X-ray Absorption Spectroscopic Investigation.

Bismuth vanadate (BiVO4) has attracted substantial attention on account of its usefulness in producing hydrogen by photoelectrochemical (PEC) water splitting. The exploitation of BiVO4 for this purpose is yet limited by severe charge recombination in the bulk of BiVO4, which is caused by the short diffusion length of the photoexcited charge carriers and inefficient charge separation. Enormous effort has been made to improve the photocurrent density and solar-to-hydrogen conversion efficiency of BiVO4. This study demonstrates that modulating the composition of the electrode and the electronic configuration of BiVO4 by decoration with silver nanoparticles (Ag NPs) is effective in not only enhancing the charge carrier concentration but also suppressing charge recombination in the solar water splitting process. Decoration with a small number of Ag NPs significantly enhances the photocurrent density of BiVO4 to an extent that increases with the concentration of the Ag NPs. At 0.5% Ag NPs, the photocurrent density approaches 4.1 mA cm−2 at 1.23 V versus a reversible hydrogen electrode (RHE) under solar simulated light illumination; this value is much higher than the 2.3 mA cm−2 of pure BiVO4 under the same conditions. X-ray absorption spectroscopy (XAS) is utilized to investigate the electronic structure of pure BiVO4 and its modification by decoration with Ag NPs. Analytical results indicate that increased distortion of the VO4 tetrahedra alters the V 3d–O 2p hybridized states. Additionally, as the Ag concentration increases, the oxygen vacancy defects that act as recombination centers in BiVO4 are reduced. In situ XAS, which is conducted under dark and solar illumination conditions, reveals that the significantly enhanced PEC performance is attributable to the synergy of modulated atomic/electronic structures and the localized surface plasmon resonance effect of the Ag nanoparticles.

Lanthanum captured in montmorillonite: Evidence of inner-sphere complexes from X-ray Absorption Spectroscopy investigations

An X-Ray Absorption Spectroscopy (XAS) study of the local structural environment of La ions hosted in montmorillonite is presented. The structural location of La ions in the host phases and whether they are incorporated in the structure or adsorbed at the surface has been assessed. Two clays from the Clay Mineral Society repository (STx and SWy) in pristine form and polymer-modified with penta-ethylen-hexamine (C10H28N6) have been studied. Ca and Na-rich montmorillonite have been contacted with 19 and 200 mM La solutions. XAS results yielded LaO distances ranging between 2.57 and 2.61 Å, compatible with literature data for La ions coordinated by water molecules. We provide evidence for the presence of a further La-Si/Al distance suggesting that La may also be bonded to the oxygen atoms on the outer surfaces of the TOT layer. Such a feature may play an important role in limiting the release/efficiency of the process. This paper is a further step in the research for REEs recovery from Electric and Electronic wastes (WEE) via a solid-liquid process, and their re-use as secondary raw materials. The knowledge of the ions-sorbent interaction mechanism, such as its nature and strength, is a fundamental information to tailor sorbents and procedures in practical applications.

The Enhanced Stability of Arsenic Coprecipitated with Magnetite during Aging: An XAS Investigation

The coprecipitation of magnetite (Fe3O4) with arsenic (As) is a potential remediation technique for As-contaminated groundwater that can be applied to meet increasingly stringent As drinking water limits. However, knowledge of the fate of As coprecipitated with magnetite during aging for extended periods is lacking, which is critical to predict the long-term efficiency of this As treatment strategy. In this work, I combined aqueous As measurements with solid-phase characterization by synchrotron-based Fe and As K-edge X-ray absorption spectroscopy (XAS) to track the transformation of magnetite and the speciation of coprecipitated As(V) or As(III) for up to a year in oxic or anoxic conditions. It was determined that the initial magnetite particle increased in crystallinity for all aging experiments, but some differences in solid-phase Fe speciation were detected depending on aging conditions. For the anoxic aging samples with initial As(V), a significant fraction (15% of the total Fe) of maghemite (a magnetic Fe oxide spinel with formula γ-Fe2O3) was identified, which was coupled to As(V) reduction [As(III) was ∼30% of the total sorbed As], suggesting electron transfer between magnetite and particle-bound As(V). In the oxic aging experiments, the initial particle crystallized, with a large fraction of Fe(III) (oxyhydr)oxides (i.e., maghemite and lepidocrocite, γ-FeOOH) in the final products. Despite increased crystallinity suggested by Fe XAS analysis, sorbed As was not released from the particles in any experiment (aqueous As never exceeded 1 μg/L). This remarkable stability of As coprecipitated with magnetite was revealed by As K-edge XAS to be largely due to the formation of distinct multinuclear As uptake modes [i.e., As(V) incorporation; hexanuclear 3C As(III) complexes]. These results demonstrate the unique potential of magnetite for long-term As sequestration.

Green reduction route via ethanol dehydrogenation and decomposition for Pd-promoted Co3O4/SBA-15 catalysts in reverse water gas shift reaction: An operando time-resolved X-ray absorption spectroscopy investigation

An alternative reduction route of Pd-promoted Co3O4 supported on SBA-15 under ethanol dehydrogenation and decomposition (ED) was studied by an operando time-resolved X-ray absorption spectroscopy (TR-XAS) to understand the insight nature of materials. The catalysts, xPd-10Co/SBA-15, were prepared by co-impregnation method where the Pd content, x = 0.2, 0.5 or 1.0 wt% and Co content = 10.0 wt%. The precursors were transformed to PdO and Co3O4 after calcination and to metallic form after reduction. The reducibility of Co3O4 to metallic Co in 1Pd-10Co/SBA-15 was 98.0%, whereas the metallic form was not produced in the absence of Pd. This catalyst also provided the highest H2 yield of 80% from ED at 500 °C. The ED-reduced 1Pd-10Co/SBA-15 was tested in reverse water gas shift reaction (RWGS) and characterized by the operando TR-XAS. The CO selectivity from CO2 was 97.8%, slightly higher than conventional H2-reduced 1Pd-10Co/SBA-15.

Digging deeper: Buried layers and interfaces studied by modified total electron yield and soft x-ray absorption spectroscopy

We report on the soft x-ray absorption spectroscopy investigation of thin film capacitors using a modified total electron yield detection mode. This mode utilizes two ammeters instead of one as commonly employed in the classical total electron yield scheme to measure photocurrents of devices under soft x-ray irradiation. The advantage of this configuration over the surface sensitive classical total electron yield mode is that it can provide information from buried layers and interfaces up to a thickness equal to the penetration depth of soft x-rays. The method can be easily adapted to existing synchrotron end stations. We investigate dielectric capacitors with dissimilar electrodes to assess the feasibility of the modified total electron yield method. Furthermore, in operando soft x-ray absorption spectroscopy measurements are performed on ferroelectric capacitors under bias and using two ammeters. The experimental results are discussed in terms of the external and internal photoemission processes and their distribution in thin film capacitors under an external bias condition. The proposed detection method opens the way to perform electronic and chemical state analyses of the buried interfaces and layers in various devices like multiferroic tunnel junctions, memristive devices, etc., during operation under an applied bias.

Synchrotron based x-ray absorption spectroscopy investigation and temperature dependent ferroelectric properties of Ni doped BaTiO3 nanostructures

In this report, the local structure geometry of BaTi1-xNixO3 (0.0 ≤ x ≤ 0.06) ceramics has been studied through synchrotron based x-ray-absorption spectroscopy, measured at the Ti K, Ba L3 and Ni K-edges at room temperature. The x-ray absorption near edge spectroscopy (XANES) at Ti K-edge confirms the TiO6 octahedron geometry of Ti atom due hybridization between Ti(3d)-O(2p) orbitals and signifies the non-centrosymmetric nature of BaTiO3 samples. However, Ti–O off-center displacement (non-centrosymmetric) is disturbed under the effect of Ni doping as a result of oxygen vacancies formation. More interestingly, XANES studies at Ni K-edge ensure successful substitution of Ni in BaTiO3 as Ni2+ ions. Extended x-ray absorption fine structure (EXAFS) data at Ni K-edge have been fitted to estimate pertinent local structural parameters of the Ni–O, Ni–Ba, Ni–Ti and Ni–Ni shells (viz. bond lengths and disorder parameters) and it also reveal that the structural disorders around the Ti sites in the doped BaTiO3 expand with Ni doping. The mixed-valence states of titanium ion, i.e., Ti4+ and Ti3+ in the doped samples were established with the x-ray photoelectron spectroscopy (XPS). Moreover, XPS divulges the creation of oxygen vacancies due to Ni doping in BaTiO3 matrix. The complementary information about the lattice vibration is analyzed through Raman studies that approve the softening of the transverse optical (TO) mode present at 515 cm−1. The temperature dependent ferroelectric studies affirm that the ferroelectricity vanishes in the doped samples due to the decrement in the off-center displacement between the Ti4+ and O2− ions in the TiO6 octahedral geometry. Differential thermal analysis (DTA) exhibits a ferroelectric tetragonal to para-electric cubic phase transition in the pristine as well as Ni doped BaTiO3 samples.

Size dependent electronic structure of LiFePO4 probed using X-ray absorption and Mössbauer spectroscopy.

We present the combined Mössbauer and X-ray absorption spectroscopy investigation of the electronic structure and local site symmetry of Fe in olivine structured LiFePO4 (LFP) with crystallite size (CS). The lattice parameters are found to contract with a decrease in CS, monotonously, whereas the electronic structural parameters exhibit two different regions with a threshold anomaly of around ≈30 nm. 57Fe Mössbauer studies reveal the coexistence of Fe2+ and Fe3+ sites and their relative concentrations are mainly determined by CS, which provides a comprehensive insight into the electronic structure of LFP at the mesoscopic level. The soft X-ray absorption unequivocally unravels the valence states of Fe 3d electrons in proximity to the Fermi level, which are prone to the local lattice distortion. The obtained spectra fingerprint the effect of CS supplying rich information on valency, lithium-ion vacancy concentration, covalency and crystal field. By comparing the spectra with the results of charge-transfer multiplet calculations, which include the full-atomic multiplet theory, we have found that the local symmetry of Fe ions is well described by the D4h point group with intermixing between eg and t2g orbitals. The unique structural and electronic properties of LFP are closely interlinked with changes in the bonding character, which shows the strong dependency on CS. The evolution of 3d states is in overall agreement with the local lattice distortion and provides the origin of the size effects on the electronic structure of olivine phosphate and other transition metal ion-containing materials.

Atomic Metal–Support Interaction Enables Reconstruction-Free Dual-Site Electrocatalyst

Real bifunctional electrocatalysts for hydrogen evolution reaction and oxygen evolution reaction have to be the ones that exhibit a steady configuration during/after reaction without irreversible structural transformation or surface reconstruction. Otherwise, they can be termed as "precatalysts" rather than real catalysts. Herein, through a strongly atomic metal-support interaction, single-atom dispersed catalysts decorating atomically dispersed Ru onto a nickel-vanadium layered double hydroxide (LDH) scaffold can exhibit excellent HER and OER activities. Both in situ X-ray absorption spectroscopy and operando Raman spectroscopic investigation clarify that the presence of atomic Ru on the surface of nickel-vanadium LDH is playing an imperative role in stabilizing the dangling bond-rich surface and further leads to a reconstruction-free surface. Through strong metal-support interaction provided by nickel-vanadium LDH, the significant interplay can stabilize the reactive atomic Ru site to reach a small fluctuation in oxidation state toward cathodic HER without reconstruction, while the atomic Ru site can stabilize the Ni site to have a greater structural tolerance toward both the bond constriction and structural distortion caused by oxidizing the Ni site during anodic OER and boost the oxidation state increase in the Ni site that contributes to its superior OER performance. Unlike numerous bifunctional catalysts that have suffered from the structural reconstruction/transformation for adapting the HER/OER cycles, the proposed Ru/Ni3V-LDH is characteristic of steady dual reactive sites with the presence of a strong metal-support interaction (i.e., Ru and Ni sites) for individual catalysis in water splitting and is revealed to be termed as a real bifunctional electrocatalyst.

The state of platinum in pyrrhotite: X-ray absorption spectroscopy study and implications for the role of Fe sulfides as platinum carriers

AbstractPyrrhotite Fe1–xS is the main sulfide component of platinum-group element (PGE) ores and commonly contains from a few tenths to a few dozen ppm of disseminated Pt. Here we report an X-ray absorption spectroscopy investigation into the state of Pt in synthetic pyrrhotite in combination with theoretical spectra modelling. The pyrrhotite crystals were obtained by means of the salt flux technique, using a eutectic mixture of alkali metal halides as the transport media. Analysis of the chemical composition of synthesised crystals showed that an increase of the temperature and sulfur fugacity yields higher concentrations of Pt in pyrrhotite. The Pt content reached 0.6 wt.% at the maximum temperature and sulfur fugacity (t= 720°C, log$f_{{\rm S}_ 2}$= –0.1) achieved in a Pt-saturated system. X-ray absorption near-edge structure (XANES) analysis of PtL3-edge spectra revealed that Pt is present in pyrrhotite in the 4+ and 2+ ‘formal’ oxidation states. Theoretical modelling of XANES and interpretation of extended X-ray absorption fine structure (EXAFS) spectra showed that Pt4+substitutes for Fe in the crystal lattice of pyrrhotite, whereas Pt2+forms PtS-like clusters disseminated in the pyrrhotite matrix. Atoms of isomorphous Pt4+are surrounded by 6 S atoms at a distance of 2.39 ± 0.02 Å. According to theoretical simulations using theFDMNESprogram, the second coordination sphere of the solid-solution Pt contains one vacancy in the Fe sublattice within the Fe-layer. The Pt2+S-like clusters can be considered as a quench product. High sulfur fugacity stabilises the solid-solution Pt and prevents the formation of the PtS-like clusters during cooling. The maximum content of the solid-solution Pt in pyrrhotite is ca. 50 times lower than in pyrite and can be approximated by a straight line in the logC(Pt)vs. 1/Tplot, it increases from 1 ppm at 350°C to 3 wt.% at 900°C.

Towards in Operando XAS Investigation of CO2 Electrolysis in Solid Oxide Cells: Synchrotron Studies of La0.3Ca0.7Fe0.7Cr0.3O3-δ Perovskites

Solid oxide cells (SOCs) are poised to provide a significant contribution to the emerging field of green technology. SOCs could form the basis for a closed loop, sustainable energy system in which fuel cells generate power efficiently and any waste products are converted back into fuel or useful products.Early solid oxide fuel cell (SOFC) systems utilized ceramic-metal composites, such as Ni-YSZ, as the fuel electrodes. Ni metal provides electronic conduction while YSZ plays the role of oxygen anion conductor. This requires the catalyst target (e.g., H2) to come into contact with both Ni and YSZ, forming a so-called triple phase boundary.Cermet systems perform well but are typically unstable under oxidizing conditions and are susceptible to passivating phenomena, such as sulfur poisoning. Since then, mixed ionic and electronic conductors (MIECs) have been developed, where a single material such as a perovskite replaces both cermet components. The gas-MIEC interface acts as a double phase boundary, theoretically providing electrochemical reaction sites on the entire surface of the electrode. This makes them less susceptible to poisoning by impurities, and the oxide composition can be tailored to improve stability in reducing or oxidizing environments. SOFCs based on mixed-conducting catalysts have shown marked performance increases over room-temperature fuel cells in ORR catalysis, often with an order of magnitude advantage in current response. Further work led to MIEC compositions being used at SOFC fuel electrodes, and more recently, as active catalysts for the carbon dioxide reduction (CO2RR) reaction in electrolysis cells (SOECs).Our research group recently demonstrated that the perovskite material, La0.3Ca0.7Fe0.7Cr0.3O3-δ (LCFCr), shows excellent stability and activity during the OER and ORR. This single composition is also highly active for the CO2RR, opening the door for reversible and symmetrical SOC devices (RSOFCs) that promise to greatly reduce device complexity. This should ease the difficulty of scaling up these technologies for industrial applications. While we have observed performance gains in both SOC modes of operation using LCFCr, we sought to better understand the underlying mechanism of catalysis in CO2 electrolysis. This has led us to begin a thorough investigation of LCFCr-based reversible SOFCs using synchrotron x-ray absorption spectroscopy (XAS), culminating with in operando studies, where CO2 electrolysis can be tracked as it happens in fully operational electrolysis cells. Harsh operating conditions have made in situ or in operando SOC studies more challenging than those for RT cells, which also share the barriers of access to electrode surfaces and the attenuation effect of feedstocks on incident energy used for spectroscopy.This presentation will introduce our initial efforts in synchrotron XAS studies of the as-synthesized LCFCr material, which was prepared by combustion synthesis of precursor metal nitrates. Synchrotron energy provided by the Canadian Light Source (CLS) was used to study powder samples of this composition; experiments were carried out at both hard (SXRMB) and soft (SGM) x-ray sources at the CLS. Preliminary experiments consisted of ex situ XAS testing of samples heat treated using conditions similar to those encountered in operation (800 °C in air or CO2). When compared to spectra of as-synthesized compositions, this provides a conventional “before and after” comparison and has demonstrated that overall changes in oxidation state and coordination environment could be observed. In situ testing was also carried out at SXRMB on La0.3Ca0.7Fe0.7Cr0.3O3-δ powder samples. Samples were placed in a “six-shot” apparatus that provided a versatile test bed for semi-realistic conditions. In these studies, materials were heated in air to 800 °C, while XANES spectra (Fe K-edge) were collected simultaneously. This process was repeated as the gas was changed to CO2, and then upon cooling. These transitionary XAS measurements allowed us to observe both structure and valence state of the material responding in real time. The results showed changes in the pre-edge feature and edge intensity that we have attributed to a change in local vacancy concentration around Fe metal centers. At each stable set of conditions, full EXAFS spectra were collected for all four metals; initial analysis suggests that chromium undergoes redox changes while the iron valence state remains largely unchanged. Together, this set of experiments is allowing us to assemble a dynamic picture of the chemical and structural state of the catalyst during operation.This study underscores the value of in situ and in operando investigation of SOC catalysts compared to traditional ex situ analysis. Insights into efficient SOC electrolysis of CO2 could give us the ability to reduce carbon emissions. It is both urgent and vital that the underlying mechanisms are understood more completely.

Elucidation of Operating Mechanism of BiFeO3 As a Negative Electrode for Na-Ion Batteries Using in Operando XAS Investigation

Sodium-ion batteries (SIBs) are gaining much attention in the global market of rechargeable batteries especially in the field of large-scale electrical energy storage systems. Considering the increasing demand for the efficient energy storage systems, it is necessary to design new electrode materials, which are capable to deliver higher reversible capacity. A wide spectra of positive electrode materials were employed in sodium ion batteries, whereas more development is required in the field of negative electrodes. Anode materials of sodium-ion batteries were mainly classified under insertion, conversion and alloying type materials1. Among the conversion type materials, Perovskite materials have gained significant attention as conversion type anode materials in sodium-ion batteries, owing to the high theoretical capacity possessed by these materials2,3.BiFeO3 is one such perovskite which possess the potential to deliver higher reversible capacity through conversion and alloying reactions4.In the present work, BiFeO3 was synthesized using a sol-gel method. Structural and morphological characterizations were done with X-ray diffraction and Field emission scanning electron microscopy techniques. Further, electrochemical studies were carried out in a sodium half-cell in the voltage range 0.01-3.00 V vs. Na+/Na. In the cyclic voltammogram, pronounced difference is observed between the first and subsequent cycles and to understand the reason behind this, elucidation of operating mechanism is required. In situ/ex situ XRD techniques are usually not sufficient to get information regarding the operating mechanism of conversion type electrode materials as these converts into metallic nanoclusters (without a long-range order) distributed in Na2O matrix during the insertion of Na+ ions. Hence, in this work, element specific X-ray absorption spectroscopic (XAS) technique was applied to elucidate the oxidation state and coordination environment changes of BiFeO3 during cycling in a sodium half-cell. Evidences for the electrochemical activity of Bi through conversion reaction (Bi3+ - Bi0) and alloying reaction (with metallic Na) during first discharge was obtained from XAS results. Further, involvement of Fe in the charge storage mechanism through conversion of its oxidized (Fe3+) form to metallic Fe was also observed, which is absent in previous literature reports. In the subsequent charging, reversible dealloying and subsequent oxidation of Bi and oxidation of Fe were noted. The Bi LIII edge and Fe K edge XAS results during second discharge reveals that similar conversion and alloying reactions occur as in the case of first discharge by reduction of Bi and Fe oxides. However, Fe and Bi oxides exists in different oxidation states at the end of first charge than in pristine BiFeO3.In addition to the elucidation of operating mechanism, the electrochemical performance of BiFeO3 was optimized by varying binder and electrolyte compositions. The best electrochemical performance was obtained when Fluoroethylene carbonate was used as an electrolyte additive. Acknowledgement A. Bhaskar gratefully acknowledge financial support from “DST-IISc Energy Storage Platform on Supercapacitors and Power Dense Devices” through the MECSP-2K17 program under grant no. DST/TMD/MECSP/2K17/20”. D. Dixon acknowledges the financial support from funding agency, Science and Engineering Board (SERB), New Delhi, India through Ramanujan Fellowship, under the grant number SB/S2/ RJN-162/2017. A. Surendran is grateful to UGC New Delhi (Ref. no.:63/CSIR-UGC NET DEC. 2017) for the UGC SRF grant and Academy of Scientific and Innovative Research (AcSIR), Ghaziabad- 201002, India. A.T acknowledges the Council of Scientific and Industrial Research (CSIR) for a senior research fellowship and Innovative Research (AcSIR), Ghaziabad- 201002. DESY, Hamburg, Germany is acknowledged for the beamtime allocation at the P65 beamline at PETRA III and we acknowledge the beamline scientist Dr. Edmund Welter for the support. The CIF, CSIR-CECRI is acknowledged for technical support with material characterization. Reference [1] Wu, C., Dou, S. X. & Yu, Y. The State and Challenges of Anode Materials Based on Conversion Reactions for Sodium Storage. Small 14, 1–20 (2018).[2] M. Nakayama, H. Ikuta, Y. Uchimoto, M. Wakihara, Changes in local structure during electrochemical Li insertion into A-site deficient perovskite oxides, La1/3NbO3, J. Phys. Chem. B,107(2003)10715-10721[3] M. Kong, K. Liu, J. Ning, J. Zhou, H. Songa, Perovskite framework NH4FeF3/carbon composite nanosheets as a potential anode material for Li and Na ions storage, J. Mater. Chem. A, 5(2017)19280-19288[4] X. Dinga, Y.Liub, Hollow bismuth ferrite combined graphene as advanced anode material for sodium-ion batteries, 30(2020)153-159

X-ray Absorption Spectroscopy Investigation into the Origins of Heterogeneity in Silica-Supported Dioxomonomolybdates

X-ray Absorption Spectroscopy Investigation into the Origins of Heterogeneity in Silica-Supported Dioxomonomolybdates

Raman and X-Ray Absorption Spectroscopy Investigations of the Structure and Ru–Mn Valence States of Li2Mn0.9Ru0.1O3

Raman and X-Ray Absorption Spectroscopy Investigations of the Structure and Ru–Mn Valence States of Li2Mn0.9Ru0.1O3

Iodine local environment in high pressure borosilicate glasses: An X-ray photoelectron spectroscopy and X-ray absorption spectroscopy investigation

• Iodine is dissolved as iodide (I − ) in high pressure borosilicate glasses. • Both alkali and alkaline-earth cations act as a charge compensator to I − species. • The absence of iodate (I 5+ ) suggests that there is a complex interplay between I − species and oxygen species within the glass structure. The 129 I radioactive isotope is a by-product of nuclear plants activity. Owing to its strong volatility, there is currently no ideal protocol to immobilize 129 I in nuclear waste borosilicate glasses. Recently, we have proposed the use of high-pressure syntheses to dissolve iodine in various glass compositions; however, I speciation and dissolution mechanism could not be determined. We have adopted an approach combining X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS) methods to determine I speciation and molecular environment in glasses containing from 0.5 to 2.5 mol.% I. The XPS spectra reveal that I is mostly dissolved as iodide (>85% I − ) with a small proportion of elemental iodine (<15% I 0 ) and the absence of iodate species (I 5+ ). For borosilicate glasses, the XAS results and subsequent spectrum simulations suggested that Na and Ca are involved in the I − vicinity with averaged derived coordination number (CN) of 3.6 and 2.0 and bond length to the nearest neighbour (r X-I ) 2.98 and 2.85 Å, respectively. These results suggest that the coexistence of both I − and I 5+ species is not requested for electric neutrality but instead, we explain the I speciation by the possible interplay with oxygen species from the borosilicate matrix. In addition, the results imply that the borosilicate network is affected by the I dissolution.