X-ray Absorption Spectroscopy Techniques Research Articles

Secondary phases characterization by SANS and XAS of an ODS ferritic steel after thermal aging at 873 K

An ODS steel with nominal composition Fe–14Cr–2W–0.4Ti-0.3Y2O3 (wt.%) was produced by mechanical alloying, compacted by hot isostatic pressing (HIP) followed by hot cross rolling (HCR). To check the effects of thermal aging at relevant temperatures of operation of fusion power plants, the alloy was thermally aged at 873 K for 2000 h. In this work, small-angle neutron scattering (SANS) and X-ray absorption spectroscopy (XAS) techniques are used for the advanced characterization of secondary phases and the oxide nanoparticle dispersion. SANS results show that the oxide nanoparticles remain stable after the thermal aging treatment. Composition of the oxide nanoparticles was identified as Y2TiO5 or Y2Ti2O7 by SANS, while non-stoichiometry was found by XAS analysis. Laves phase precipitation after the thermal aging treatment is further confirmed by SANS, from the magnetic anisotropic contribution to the scattering intensity associated to this metallic phase, and by XANES.

PINK: a tender X-ray beamline for X-ray emission spectroscopy.

A high-flux beamline optimized for non-resonant X-ray emission spectroscopy (XES) in the tender X-ray energy range has been constructed at the BESSY II synchrotron source. The beamline utilizes a cryogenically cooled undulator that provides X-rays over the energy range 2.1 keV to 9.5 keV. This energy range provides access to XES [and in the future X-ray absorption spectroscopy (XAS)] studies of transition metals ranging from Ti to Cu (Kα, Kβ lines) and Zr to Ag (Lα, Lβ), as well as light elements including P, S, Cl, K and Ca (Kα, Kβ). The beamline can be operated in two modes. In PINK mode, a multilayer monochromator (E/ΔE ≃ 30-80) provides a high photon flux (1014 photons s-1 at 6 keV and 300 mA ring current), allowing non-resonant XES measurements of dilute substances. This mode is currently available for general user operation. X-ray absorption near-edge structure and resonant XAS techniques will be available after the second stage of the PINK commissioning, when a high monochromatic mode (E/ΔE ≃ 10000-40000) will be facilitated by a double-crystal monochromator. At present, the beamline incorporates two von Hamos spectrometers, enabling time-resolved XES experiments with time scales down to 0.1 s and the possibility of two-color XES experiments. This paper describes the optical scheme of the PINK beamline and the endstation. The design of the two von Hamos dispersive spectrometers and sample environment are discussed here in detail. To illustrate, XES spectra of phosphorus complexes, KCl, TiO2 and Co3O4 measured using the PINK setup are presented.

Unveiling nano-scale chemical inhomogeneity in surface oxide films formed on V- and N-containing martensite stainless steel by synchrotron X-ray photoelectron emission spectroscopy/microscopy and microscopic X-ray absorption spectroscopy

Nano-scale chemical inhomogeneity in surface oxide films formed on a V- and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron- based hard X-ray Photoelectron emission spectroscopy (HAXPES) and microscopy (HAXPEEM) as well as microscopic X-ray absorption spectroscopy (m-XAS) techniques. The results reveal the inhomogeneity in the oxide films on the micron-sized Cr2N- and VN-type particles, while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600 °C. The oxide film formed on Cr2N-type particles is rich in Cr2O3 compared with that on the martensite matrix and VN-type particles. With the increase of tempering temperature, Cr2O3 formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.

Synchrotron Radiation Based X-ray Absorption Spectroscopy: Fundamentals and Applications in Photocatalysis.

Photocatalysis is one of the most promising green technologies to utilize solar energy for clean energy achievement and environmental governance. There is a knotty problem to rational designing high-performance photocatalyst, which largely depends on an in-depth insight into their structure-activity relationships and complex photocatalytic reaction mechanisms. Synchrotron radiation based X-ray absorption spectroscopy (XAS) is an important characterization method for photocatlayst to offer the element-specific key geometric and electronic structural information at the atomic level, on this basis, time-resolved XAS technique has a huge impact on mechanistic understanding of photochemical reaction owing to their powerful ability to probe, in real-time, the electronic and geometric structures evolution within photocatalysis reactions. This review will focus on the fundamentals of XAS and their applications in photocatalysis. The detailed applications obtained from XAS is described through the following aspects: 1) identifying local structure of photocatalyst; 2) uncovering in situ structure and chemical state evolution during photocatalysis; 3) revealing the photoexcited process. We will provide an in depth understanding on how the XAS method can guide the rational design of highly efficient photocatalyst. Finally, a systematic summary of XAS and related significance is made and the research perspectives are suggested.

Correlation of electronic structure and magnetic properties of [formula omitted] nanostructure using synchrotron soft XAS

The present study reports crystalline structure, electronic structure and magnetic properties for nanoparticles undoped CeO2 and Ce1-xSmxO2 (x = 0.02 to 0.10, @ 0.02). The nanoparticle samples are synthesized by the co-precipitation method. XRD data shows the successful incorporation of Sm3+ ions at Ce4+ sites in the face-centered cubic (fcc) lattice. The soft X-ray absorption spectroscopy technique is utilized to get an insightful overview of electronic structural properties due to structural defects, chemical states and the development of oxygen vacancies in Ce1-xSmxO2 nanoparticles. The soft XAS spectra show a significant Ce and Sm peak in the M4,5 domain, along with the well-defined O K-edge peak. Analysis of Ce M4,5-edges indicates that Ce-ions have both 3 + and 4 + oxidation states. With the incorporation of Sm+3 ions, there is a reduction of Ce4+ states and oxidation of Ce3+ states, as well as a substantial increase in oxygen vacancy concentration. The room-temperature magnetic properties of Ce1-xSmxO2 nanoparticles reveal ferromagnetic behavior. The origin of ferromagnetism is explained by F-center exchange (FCE) coupling mechanisms mediated via development of oxygen vacancy and defects.

In-situ and operando Grazing Incidence XAS: a novel set-up and its application to model Pd electrodes for alcohols oxidation

Abstract In this article, we present an in-situ and operando time-resolved X-ray Absorption Spectroscopy (XAS) technique which exploits a combination of Grazing Incidence XAS (GIXAS) and Fixed Energy X-ray Absorption Voltammetry (FEXRAV), the Grazing Incidence FEXRAV (GI-FEXRAV). A case-study is also outlined. Palladium ultra-low loadings were deposited above Au polycrystalline iso-oriented substrates adopting three different deposition methods: surface-controlled electrochemical methods, direct electrodeposition, and physical vapour deposition (PVD). These catalytical surfaces were prepared for the investigation by GI-FEXRAV of the Pd oxidation/dissolution phenomenon that could occur when the metal is used in the anodic compartment of Direct Alcohol Fuel Cells (DAFCs) or in electrochemical reformers. Moreover, we report a robust, low cost and versatile procedure to obtain wide and flat iso-oriented gold substrates that can mimic monocrystalline gold (1 1 1) in the electrochemical response. The use of GI-FEXRAV for the operando characterization of the catalysts, in conjunction with the designed experimental cell and our flexible Au-based electrochemical substrates show an invaluable potential in the operando study of fundamental phenomena in heterogeneous electrocatalysis model systems and, due to its versatility, paves the way to further studies on a wide selection of electrochemical systems.

New Design PdNi Heterogeneous Nanocatalysts for the Direct Synthesis of Hydrogen Peroxide

Hydrogen peroxide (H2O2) is a widely used chemical as an eco-friendly oxidizing agent, with water being the only byproduct of oxidation in applications like bleaching pulp and paper, making electronic semiconductors, chemical and detergent synthesis, and wastewater treatment. The direct synthesis approach is preferred to provide the environmentally friendly production of H2O2 for market requirements. Bimetallic PdNi nanocatalysts were chosen for this study because of their catalytic activity and the structural characteristics of the material system. First, for the development of order-structured bimetallic PdNi nanocatalysts based on mesoporous carbon template after hydrogen-assisted heat treatment at 750∘C. The transformation of the disordered structure into ordered intermetallically structured PdNi alloys with higher alloying extents was confirmed by X-ray absorption spectroscopy (XAS) and high-resolution transition electron microscopy (HR-TEM). Then, to improve the oxygen oxidation reaction, two-electron pathway selectivity was used by TiO2-C as a support-ordered structure material to facilitate strong metal-support interactions. XAS and X-ray photoelectron spectra (XPS) techniques show more clear evidence of metal-support interactions with electron transfer from defects in the TiO2-C support to the ordered alloyed PdNi nanocatalysts, resulting in record productivity and selectivity of H2O2 production at ambient conditions. The results demonstrated in this study will enlighten a reliable design of new heterogeneous nanocatalysts with ordered structure. Electron transfer between hybrid support and active sites can clarify the catalytic behavior and prompt further research during the direct synthesis of hydrogen peroxide.
 Keywords: hydrogen peroxide, direct synthesis, heterogeneous nanocatalysts PdNi, TiO2-C

Crystalline Magnetic Anisotropy in High Entropy (Fe, Co, Ni, Cr, Mn)3O4 Oxide Driven by Single‐Element Orbital Anisotropy

AbstractThe design of multicomponent materials has captured considerable attention due to its extraordinary ability to tailor functional properties. However, how a single element affects the behavior of the overall material has yet to be explored in depth. In this study, the heteroepitaxy of high entropy (Fe, Co, Ni, Cr, Mn)3O4 films with varying strain states are investigated in magnetic performance. It is discovered that the high entropy oxide thin film with compressive strain exhibits an effect of crystalline magnetic anisotropy. Diverse analyses provide a detailed understanding of high entropy magnetic oxide systems, including X‐ray diffraction, reciprocal space mapping, macroscopic magnetic characterization, X‐ray absorption spectroscopy (XAS), etc. Notably, the element‐specific XAS technique proves effective in uncovering the origin of the crystalline magnetic anisotropy. Due to the substrate‐induced epitaxial strain, the eg orbitals of Mn3+ form different energy levels, leading to different preferred electron occupancy. The exploration of magnetic properties in epitaxial high entropy oxide film is then raveled. By navigating the complexities introduced by the random atom distribution and intricate magnetic interactions, this study pioneers novel methodologies for probing the core physics of high entropy oxides.

Process Intensification and Performance Assessment of Sputtered Gadolinium Doped Ceria (GDC) Barrier Layer in Large-Area Solid Oxide Fuel Cell Short Stack

In recent years, Gadolinium Doped Ceria (GDC) barrier layers have been reported to enhance the performance of Solid Oxide Fuel Cells (SOFCs)by reducing cathode/electrolyte interface diffusion and improving ionic conductivity. Prior investigations have demonstrated that GDC thin film sputtered at room-temperature yields substantial enhancements in Solid Oxide Fuel Cells (SOFCs).This enhancement is evidenced by a noteworthy increase in output current (+78%) and a considerable reduction in ohmic resistance (up to -42%), compared to conventionally screen-printed industrial SOFCs. To probe the intricate interplay between morphology and stoichiometry, which fundamentally determines the Ce3+/Ce4+ ratio governing both ionic and electronic conductivity, this study utilized quantitative X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS) techniques. Results revealed that annealing parameters played a role in the number of available oxygen vacancies in the oxygen-reduction reaction (ORR), inducing different changes in the investigated samples. Non-destructive investigations utilizing Distribution of Relaxation Time (DRT) analysis were conducted on two short stacks with varying thickness, employing different sputtering Modalities. These studies revealed that thickness significantly influences the ultimate performance.

Real-time observation of polarization dependence of soft x-ray absorption spectrum during chemical reaction under near-ambient pressure conditions.

The real-time observation of the polarization dependence of soft x-ray absorption spectra during chemical reactions is realized by combining the fluorescence-yield wavelength-dispersive x-ray absorption spectroscopy technique with a 10Hz switching between horizontal and vertical polarizations. The soft x-ray absorption spectra for boththe horizontal and vertical polarizations are recorded every 100ms with a time difference of 50ms, which enables the real-time observation of changes in the anisotropic structure around the surface. The technique is applied to the oxidation reaction of a cobalt thin film under an air pressure of up to 25Pa, and it is suggested that an anisotropic structure appears during the growth of the cobalt oxide species. By using the developed technique, it is expected that the changes in the anisotropic structures, such as molecular orientations, are observed during chemical reactions under near-ambient pressure conditions, which gives a deeper insight into the understanding of the reaction mechanism.

Texture, electronic and magnetic states of Mn atoms in polycrystalline MnSi thin films facing a c-sapphire substrate studied by soft X-ray magnetic circular dichroism

Polycrystalline MnSi is a highly efficient magnetic skyrmionic material and information carriers for future spintronic devices, deposited on a c-cut sapphire substrate by magnetron sputtering with a low base pressure. Due to their fascinating crystal structures and spin textures these Mn-based silicides are most extensively studied now a days. In order to study the appearance of any impure phases like MnxSiy, hysteresis behavior and the inception of ferromagnetic/superparamagnetic domains present in the MnSi film, we have performed X-ray diffraction (XRD), XRD pole figures in stereographic projection, vibrating sample magnetometry and powerful element specific X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism techniques. The room temperature hysteresis curve points towards the phenomenon of long-range ferromagnetic ordering. The Mn L2,3 edge XAS spectra did not show a Mn2+-like multiplet structure. The overall magnetization increases with the increase in applied magnetic field from 0.1 T to 2 T on MnSi thin film. The observed spin and orbital magnetic moments ∼ 0.03 ̶ 0.1 μB and 0.01 to 0.04 μB, respectively.

Photovoltaic efficiency enhancement via magnetism

The efficiency of photovoltaic cells has long been a subject of intense concern and research. Diverse photovoltaic cell types have been developed, including crystalline silicon cells (achieving up to 27.6% efficiency), multijunction cells (reaching up to 47.4% efficiency), thin film cells (attaining up to 23.6% efficiency), and emerging photovoltaic cells (exhibiting up to 33.7% efficiency). Despite advancements, achieving high efficiency on an industrial scale remains a significant challenge due to factors like charge carrier recombination rate, defects, temperature’s influence, etc. Numerous approaches have been explored to address these challenges, encompassing strategies such as incorporation of nanoparticle within the active layer, studying transport properties and defects using ion beams, utilizing magnetite materials, and leveraging the application of magnetic fields. The influence of a magnetic field can amplify the generation of charge transfer states exhibiting triplet characteristics, increasing the charge separation time. However, magnetic fields introduce spin-based effects, enabling the investigation of interactions between electron spins and magnetic fields through state-of-an-art synchrotron radiation techniques like XMCD. Several innovative cell configurations have reported substantial efficiency enhancements under the influence of magnetic fields. Examples include TiO2-BiFeO3 dye-sensitized cells, polymer-based cells with Fe3O4@PANI additives integrated into TiO2-based dye-sensitized cells, and the incorporation of Fe-doped SnO2 within the active layer of heterojunction organic solar cells. In this perspective review, the profound impact of magnetism on enhancing efficiency in photovoltaic cells has been analysed and the utilization of advanced X-ray absorption spectroscopic techniques to probe and comprehend these intricate effects.

Origin of Enhancement of Orbital Magnetic Moment in SiO2-Coated Fe3O4 Nanocomposites Studied by X-ray Magnetic Circular Dichroism.

In this study, magnetic Fe3O4 nanoparticles (NPs) were dispersed uniformly by varying the thickness of the SiO2 coating, and their electronic and magnetic properties were investigated. X-ray diffraction confirmed the structural configuration of monophase inverse-spinel Fe3O4 NPs in nanometer size. Scanning electron microscopy revealed the formation of proper nonporous crystallite particles with a clear core-shell structure with silica on the surface of Fe3O4 NPs. The absorption mechanism studied through the zeta potential indicates that SiO2-coated Fe3O4 nanocomposites (SiO2@Fe3O4 NCs) possess electrostatic interactions to control their agglomeration in stabilizing suspensions by providing a protective shield of amorphous SiO2 on the oxide surface. High-resolution transmission electron microscopy images demonstrate a spherical morphology having an average grain diameter of ∼11-17 nm with increasing thickness of SiO2 coating with the addition of a quantitative presence and proportion of elements determined through elemental mapping and electron energy loss spectroscopy studies. Synchrotron-based element-specific soft X-ray absorption spectroscopy and X-ray magnetic circular dichroism (XMCD) techniques have been involved in the bulk-sensitive total fluorescence yield mode to understand the origin of magnetization in SiO2@Fe3O4 NCs. The magnetization hysteresis of Fe3O4 was determined by XMCD. At room temperature, the magnetic coercivity (Hc) is as high as 1 T, which is about 2 times more than the value of the thin film and about 5 times more pronounced than that of NPs. For noninteracting single-domain NPs with the Hc spread from 1 to 3 T, the Stoner-Wohlfarth model provided an intriguing explanation for the hysteresis curve. These curves determine the different components of Fe oxides present in the samples that derive the remnant magnetization involved in each oxidation state of Fe and clarify which Fe component is responsible for the resultant magnetism and magnetocrystalline anisotropy based on noninteracting single-domain particles.

Atomically dispersed copper-nickel electrocatalyst for highly selective electroreduction of CO2 at a wide potential range

Designing and synthesising electrocatalysts with low overpotential, high activity, selectivity, and stability for the CO2 reduction reaction (CO2RR) is crucial for addressing environmental challenges and realising the artificial carbon cycle. In this study, we successfully synthesised a nitrogen-doped carbon-supported diatomic electrocatalyst comprising atomically dispersed CuN4 and NiN4 bimetallic centers. This was confirmed through extensive characterisation using high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption spectroscopy techniques. The as-synthesised CBN-CuNi electrocatalyst exhibited exceptional selectivity and stability in CO2RR. Over a wide potential range from − 0.60 to − 1.10 V vs RHE, CBN-CuNi maintained over 90% Faraday efficiency for CO (FECO) production. Notably, at − 0.9 V vs RHE, it achieved a remarkable selectivity with a maximum FECO of 97.9%, surpassing single metal catalysts, including CBN-Ni and CBN-Cu. Furthermore, CBN-CuNi demonstrated outstanding stability, sustaining over 90% FECO production for 40 h of continuous electrolysis, surpassing many existing electrocatalysts. These findings highlight the potential of the as-synthesised bimetallic electrocatalyst CBN-CuNi in the electrochemical reduction of CO2 to CO, contributing to advancing the artificial carbon cycle and addressing environmental concerns.

Exploring the cellular surface polysaccharide and root nodule symbiosis characteristics of the rpoN mutants of Bradyrhizobium sp. DOA9 using synchrotron-based Fourier transform infrared microspectroscopy in conjunction with X-ray absorption spectroscopy.

The functional significance of rpoN genes that encode two sigma factors in the Bradyrhizobium sp. strain DOA9 has been reported to affect colony formation, root nodulation characteristics, and symbiotic interactions with Aeschynomene americana. rpoN mutant strains are defective in cellular surface polysaccharide (CSP) production compared with the wild-type (WT) strain, and they accordingly exhibit smaller colonies and diminished symbiotic effectiveness. To gain deeper insights into the changes in CSP composition and the nodules of rpoN mutants, we employed synchrotron-based Fourier transform infrared (SR-FTIR) microspectroscopy and X-ray absorption spectroscopy. FTIR analysis of the CSP revealed the absence of specific components in the rpoN mutants, including lipids, carboxylic groups, polysaccharide-pyranose rings, and β-galactopyranosyl residues. Nodules formed by DOA9WT exhibited a uniform distribution of lipids, proteins, and carbohydrates; mutant strains, particularly DOA9∆rpoNp:ΩrpoNc, exhibited decreased distribution uniformity and a lower concentration of C=O groups. Furthermore, Fe K-edge X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses revealed deficiencies in the nitrogenase enzyme in the nodules of DOA9∆rpoNc and DOA9∆rpoNp:ΩrpoNc mutants; nodules from DOA9WT and DOA9∆rpoNp exhibited both leghemoglobin and the nitrogenase enzyme. IMPORTANCE This work provides valuable insights into how two rpoN genes affect the composition of cellular surface polysaccharides (CSPs) in Bradyrhizobium sp., which subsequently dictates root nodule chemical characteristics and nitrogenase production. We used advanced synchrotron methods, including synchrotron-based Fourier transform infrared (SR-FTIR) microspectroscopy and X-ray absorption spectroscopy (XAS), for the first time in this field to analyze CSP components and reveal the biochemical changes occurring within nodules. These cutting-edge techniques confer significant advantages by providing detailed molecular information, enabling the identification of specific functional groups, chemical bonds, and biomolecule changes. This research not only contributes to our understanding of plant-microbe interactions but also establishes a foundation for future investigations and potential applications in this field. The combined use of the synchrotron-based FTIR and XAS techniques represents a significant advancement in facilitating a comprehensive exploration of bacterial CSPs and their implications in plant-microbe interactions.

X-ray absorption fine structure (XAFS)-based radionuclide research at the KIT Light Source

Abstract. In the past two decades, X-ray absorption spectroscopy (XAS) and related synchrotron-based radionuclide speciation techniques have become indispensable, supporting open issues in fundamental radiochemistry and nuclear waste disposal alike. Physicochemical structure information – encoded in the element-specific X-ray absorption fine structure (XAFS) – is obtained by the precise determination of the linear mass absorption coefficient μ(E) of a specimen in an X-ray energy window ΔE encompassing an electronic bonding level of a selected atom type. The characteristic modulations of μ(E) in the vicinity of an “absorption edge” (i.e., the steeply rising absorption probability of photons tuned to the binding energy of inner shell “core” electrons) are attributed to electronic transitions into unoccupied states due to the photoelectric effect. While absorption features close to the edge (arising from excitations into molecular orbitals or empty band structure levels close to the Fermi level) are generally denoted as an X-ray absorption near-edge structure (XANES), the scattering states at higher excitation energies are causing the well-known extended X-ray absorption fine structure (EXAFS). EXAFS oscillations of the post-edge μ(E) are caused by the periodicity of the constructive and destructive interference of outbound and backscattered inbound photoelectron waves (superimposing at the absorbing atom site) when continuously increasing the excitation energy. Quantitative analysis of EXAFS data based on electron scattering theory is a well-established short-range structural probe, providing precise values of interatomic distances (between the absorber atom and its neighbors) and additional information on the type, number, and ordering of neighbor atoms within a local cluster. Recent significant advancements in the quantum theoretical description of core-excited final states have been successful in overcoming persisting ambiguities in XANES data interpretation. Meanwhile, although there are more than 50 synchrotron radiation centers operational in the world, facilities with specialized beamline infrastructure and safety protocols to allow experiments on radioactive samples with activities beyond the exemption limits are still scarce. At the KIT Light Source (at the Karlsruhe Institute of Technology, Karlsruhe, Germany), the Institute for Nuclear Waste Disposal (Institut für Nukleare Entsorgung, INE) operates two beamline end-stations dedicated to the investigation of radionuclide materials by XAFS spectroscopy and related techniques, i.e., the INE-Beamline (operational since 2005) and the ACT station of the CAT-ACT (CATalysis and ACTinide) wiggler beamline (operational since 2016). Samples with total activities amounting to 1.0×106 times the isotope specific exemption limits and 200 mg of fissile isotopes 235U and 239Pu are feasible at both beamlines. Highly versatile detection systems and sample holders – generally avoiding extensive shielding or sample handling in a glove box – have been conceived since the initial commissioning of the beamlines and have enabled unique XAFS measurements such as the first ever investigation of aqueous technetium species at the Tc L3 edge. Investigations of highly radioactive specimens (e.g., spent nuclear fuel or nuclear waste glass fragments) are feasible, regardless of the actual contact dose rate if the radiation field is limited to a few microsieverts per hour at the edge of the experimental table.

Combining X-ray Absorption and NMR spectroscopies to investigate a chemical reaction in solution

Transition metal chemistry in solution is central to key processes in biology and catalysis. Achieving accurate knowledge on the structural and electronic properties of the relevant reaction intermediates requires the use of innovative and complementary spectroscopic probes. Herein, we combine X-ray Absorption Spectroscopy (XAS) and 1H-NMR to investigate the exchange reaction between two prototypical Cu coordination complexes in solution. By means of multivariate and theoretical analyses, we identify the number, nature and concentration time evolution of the relevant reaction intermediates and quantitatively determine their structures. The XAS and NMR techniques are proven to be complementary experimental tools to track the fate of both the metal and organic portions of reactive systems involving transition metals. The employed combined experimental and theoretical method may be useful in the study of reactive systems involving intermediates that may be labile or silent to conventional detection.

X-ray absorption spectroscopy study of the electronic and structural properties of hexavalent chromium adsorbed by volcanic ashes

X-ray absorption spectroscopy (XAS) was used to characterize the volcanic ash (VA) materials as a low-cost and natural environmental adsorbent for the sorption of Cr (VI). The batch adsorption method was employed to synthesize the sample of chromium (VI) sorbed by VA. The results showed that the Cr-VA material is in the chromium oxidation state (III) and can be described as a composition of Cr2O3 (47.9%), FeCr2O4 (45.2%), and Na2Cr2O7 (6.9%). The promotion of the 1s Cr core electron implies the electronic transitions 1s to 3d(t2g) and 1s to 3d(eg). The first and second shells in the Cr-VA material were coordinated with the oxygen and chromium atoms in a distorted geometrical arrangement. The adsorption mechanism was associated with the chemical reduction of Cr (VI) to Cr (III) via an ion-exchange process. The XAS technique significantly contributes to the characterization of environmental VA, which can be proposed as an economical and alternative adsorbent for the sorption of Cr from contaminated wastewater.

Deciphering structural changes in LiNixMnyCozO2 cathodes of Li ion batteries during cycling: Experimental and theoretical investigations

Layered oxide material LiNixMnyCozO2 is emerging out as promising cathode for new generation of Li-ion batteries, especially as power sources for electric vehicles and plug-in hybrid vehicles. In this work, structural and electronic changes occurring in LiNixMnyCozO2 (LNMC) cathode materials during charge/discharge cycle of the battery is studied over a wide composition range using in-situ X-ray diffraction (XRD) and in-situ X-ray absorption spectroscopy (XAS) techniques. While in-situ XRD measurements decipher the overall structural changes during the charging/discharging cycles, in-situ element specific XAS measurements reveal site specific information on electronic and local structural changes. It has been found that for the LNMC samples the major charge compensation at the metal site during charging or Li ion de-intercalation is achieved by oxidation of Ni2+ ions without significant change in the oxidation state of Co or Mn ions. It is also found that local structure around Ni undergoes reversible change during charging and discharging cycles whereas local structure around Co or Mn sites show no significant change. Moreover, it has been found that local structural changes at Ni sites in the samples with higher Ni concentrations are much less compared to that in the samples with lower Ni concentrations during charging/discharging cycles, the result being corroborated by ab-initio theoretical simulations also. This is a new finding and would have significant implications in determining the optimum composition of LNMC electrodes of Li ion batteries for commercial applications.

Tuning the atomic configuration environment of MnN4 sites by Co cooperation for efficient oxygen reduction

Carbon-based N-coordinated Mn (Mn-Nx/C) single-atom electrocatalysts are considered as one of the most desirable non-precious oxygen reduction reaction (ORR) candidates due to their insignificant Fenton reactivity, high abundance, and intriguing electrocatalytic performance. However, current Mn-Nx/C single-atom electrocatalysts suffer from high overpotentials because of their low intrinsic activity and unsatisfactory chemical stability. Herein, through an in-situ polymerization-assisted pyrolysis, the Co as a second metal is introduced into the Mn-Nx/C system to construct Co, Mn-Nx dual-metallic sites, which atomically disperse in N-doped 1D carbon nanorods, denoted as Co, Mn-N/CNR and hereafter. Using electron microscopy and X-ray absorption spectroscopy (XAS) techniques, we verify the uniform dispersion of CoN4 and MnN4 atomic sites and confirm the effect of Co doping on the MnN4 electronic structure. Density functional theory (DFT) calculations further elucidate that the energy barrier of rate-determining step (*OH desorption) decreases over the 2 N-bridged MnCoN6 moieties related to the pure MnN4. This work provides an effective strategy to modulate the local coordination environment and electronic structure of MnN4 active sites for improving their ORR activity and stability.