Combined X-ray Absorption Spectroscopy Research Articles

Towards Atomically Precise Supported Catalysts from Monolayer-Protected Clusters: The Critical Role of the Support.

Controlling the size and uniformity of metal clusters with atomic precision is essential for fine‐tuning their catalytic properties, however for clusters deposited on supports, such control is challenging. Here, by combining X‐ray absorption spectroscopy and density functional theory calculations, it is shown that supports play a crucial role in the evolution of monolayer‐protected clusters into catalysts. Based on the acidic nature of the support, cluster‐support interactions lead either to fragmentation of the cluster into isolated Au–ligand species or ligand‐free metallic Au0 clusters. On Lewis acidic supports that bind metals strongly, the latter transformation occurs while preserving the original size of the metal cluster, as demonstrated for various Aun sizes. These findings underline the role of the support in the design of supported catalysts and represent an important step toward the synthesis of atomically precise supported nanomaterials with tailored physico‐chemical properties.

Role of point and line defects on the electronic structure of LaAlO3/SrTiO3 interfaces

Realization of heterostructures containing multiple two-dimensional electron liquids requires a fine control of the fabrication process. Here, we report a structural and spectroscopy study of LaAlO3/SrTiO3/LaAlO3 trilayers grown on the SrTiO3 substrate by pulsed-laser deposition. Scanning transmission electron microscopy with the help of ab initio calculations reveals that antisite defects associated with oxygen vacancies are primarily present in the SrTiO3 film (STO-f) close to the p-type interface (STO-f/LaAlO3), while oxygen vacancies prevail close to the top n-type interface (LaAlO3/STO-f). At the same interface, misfit dislocations relax the tensile strain of the top LaAlO3 layer. Combining x-ray absorption spectroscopy, x-ray linear dichroism, resonant photoemission spectroscopy, and electron energy loss spectroscopy, we observe that the 3d orbital reconstruction at the interface between LaAlO3 and the SrTiO3 substrate is confined over a few interfacial Ti planes while, at the top n-type interface (LaAlO3/STO-f), the absence of a dichroic signal can be related to the blurring of the interfacial orbital reconstruction due to the heterogeneity of defects.

Ultra-Sensitive and Selective Detection of Arsenic(III) via Electroanalysis over Cobalt Single-Atom Catalysts.

Achieving highly sensitive and selective detection of trace-level As(III) and clarifying the underlying mechanism is still a intractable problem. The electroanalysis of As(III) relies on the electrocatalytic ability of the sensing interface. Herein, we first adopt single-atom catalysts as the electrocatalyst in As(III) detection. Cobalt single-atoms anchored on nitrogen-doped carbon material (Co SAC) were found to have an extraordinary sensitivity of 11.44 μA ppb-1 with excellent stability and repeatability, which so far is the highest among non-noble metal nanomaterials. Co SAC also exhibited a superior selectivity toward As(III) compared with some bivalent heavy metal ions (HMIs). Combining X-ray absorption spectroscopy (XAFS), density functional theory (DFT) calculation, and reaction kinetics simulation, we demonstrated that Co single atoms stabilized in N2C2 support serve as active sites to catalyze H3AsO3 reduction via the formation of Co-O hybridization bond, leading to a lower energy barrier, promoting the breakage of As-O bonds. Importantly, the first electron transfer is the rate-limiting step of arsenic reduction and is found to be more favorable on Co-SAC both thermodynamically and kinetically. This work not only expands the potential applicaiton of single-atom catalysts in the detection and treatment of As(III), but also provides atomic-level catalytic insights into HMIs sensing interfaces.

Cationic disorder: A pathway for demonstrating inverse exchange bias in Gd2CoRuO6

We report here the observation of the inverse exchange bias phenomenon in the ferrimagnetic double-perovskite ${\mathrm{Gd}}_{2}{\mathrm{CoRuO}}_{6}$. The compound crystallizes in a monoclinic structure (space group $P{2}_{1}/n$), and it undergoes long-range magnetic ordering below ${T}_{C}=60$ K. The ferrimagnetic state of the sample is manifested through magnetization reversal at low temperature. In order to corroborate the role of local structure on the magnetic properties of ${\mathrm{Gd}}_{2}{\mathrm{CoRuO}}_{6}$, we have performed a combined magnetization and x-ray absorption spectroscopy study on two different samples prepared through different cooling protocols (slow cooling and furnace cooling). Extended x-ray absorption fine-structure analysis indicates the presence of strong antisite disorder between Co and Ru in both samples. However, the slow-cooled sample shows completely random antisite disorder, whereas, small Co- and Ru-rich patches appear in the furnace-cooled sample. In both samples, a significant amount of mixed valency in Co and Ru ions is evident from our x-ray absorption near-edge structure. The antiparallel ordering along with different temperature dependence of the three magnetic sublattices, Gd, Co, and Ru, can be responsible for negative magnetization, whereas the inverse exchange bias effect can be attributed to the mixed interfacial coupling between adjacent magnetic nanoclusters. The difference in local structure can nicely be accounted for by the observed variations of the magnetic properties between two samples of ${\mathrm{Gd}}_{2}{\mathrm{CoRuO}}_{6}$.

Understanding the redox process upon electrochemical cycling of the P2-Na0.78Co1/2Mn1/3Ni1/6O2 electrode material for sodium-ion batteries

Rechargeable sodium-ion batteries have recently attracted renewed interest as an alternative to Li-ion batteries for electric energy storage applications, because of the low cost and wide availability of sodium resources. Thus, the electrochemical energy storage community has been devoting increased attention to designing new cathode materials for sodium-ion batteries. Here we investigate P2- Na0.78Co1/2Mn1/3Ni1/6O2 as a cathode material for sodium ion batteries. The main focus is to understand the mechanism of the electrochemical performance of this material, especially differences observed in redox reactions at high potentials. Between 4.2 V and 4.5 V, the material delivers a reversible capacity which is studied in detail using advanced analytical techniques. In situ X-ray diffraction reveals the reversibility of the P2-type structure of the material. Combined soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering demonstrates that Na deintercalation at high voltages is charge compensated by formation of localized electron holes on oxygen atoms.

Combined micro X-ray absorption and fluorescence spectroscopy to map phases of complex systems: the case of sphalerite

Combining micro-X-ray absorption spectroscopy (μXAS) and micro-X-ray fluorescence spectroscopy (μXRF) is a promising approach for the investigation of complex multi-phase systems. In this work, we have employed this approach to investigate natural sphalerite, the most common form of Zinc Sulfide. Spatially resolved elemental distribution maps of common 3d metal atoms (Zn, Cu, Ni, Co, and Fe) are superimposed with chemical speciation and structural parameter maps in order to understand the sphaleriteore-formation process and metamorphosis. Chemical speciation and structural parameters have been obtained by analyzing the μXAS spectra collected in several representative points of the sample, after μXRF mapping. In the present case, this X-ray based approach has permitted to determine the spatial distribution of the Zn species in sphalerite. The presence of two main zincite and smithsonite inclusions has been established, with the latter located close to copper impurity center. Since copper is known to remarkably reduce the corrosion resistance of zinc, resulting in the formation of carbonate as the corrosion product, this implies a possible role of Cu in the growth of the carbonate inclusions. The results obtained highlight the efficiency of this method in univocally identifying the spatial distribution of phases in complex systems, thanks to the simultaneous access to complementary information.

Boosting Oxygen Evolution Reaction by Creating Both Metal Ion and Lattice-Oxygen Active Sites in a Complex Oxide.

Developing efficient and low-cost electrocatalysts for the oxygen evolution reaction (OER) is of paramount importance to many chemical and energy transformation technologies. The diversity and flexibility of metal oxides offer numerous degrees of freedom for enhancing catalytic activity by tailoring their physicochemical properties, but the active site of current metal oxides for OER is still limited to either metal ions or lattice oxygen. Here, a new complex oxide with unique hexagonal structure consisting of one honeycomb-like network, Ba4 Sr4 (Co0.8 Fe0.2 )4 O15 (hex-BSCF), is reported, demonstrating ultrahigh OER activity because both the tetrahedral Co ions and the octahedral oxygen ions on the surface are active, as confirmed by combined X-ray absorption spectroscopy analysis and theoretical calculations. The bulk hex-BSCF material synthesized by the facile and scalable sol-gel method achieves 10 mA cm-2 at a low overpotential of only 340 mV (and small Tafel slope of 47 mV dec-1 ) in 0.1 m KOH, surpassing most metal oxides ever reported for OER, while maintaining excellent durability. This study opens up a new avenue to dramatically enhancing catalytic activity of metal oxides for other applications through rational design of structures with multiple active sites.

Chemical nature of zinc in size fractionated particulate matter from residual oil combustion - A comparative study

Although zinc is ubiquitous in ambient particulate matter (PM), exposure to size fractionated residual oil fly ash (ROFA) PM is of particular concern due to several studies implicating particle zinc in mortality, adverse respiratory and cardiac effects. The lack of zinc speciation data is an impediment to our understanding of the biological mechanism of Zn induced toxicity. ROFA PM2.5+ samples (i.e. particle with aerodynamic diameter >2.5 μm) are prepared in a small 732 kW practical fire tube boiler by combusting one No. 5 and three No. 6 residual oil(s) of varying sulfur and ash contents. The combined X-ray absorption spectroscopy and selective extraction method is used to determine the Zn speciation in PM2.5+ samples. The Zn speciation in ROFA PM2.5 (i.e. particle with aerodynamic diameter <2.5 μm) samples, reported earlier, is included here for comparison purposes. The data show that zinc sulfate is predominant in both fractions. In addition, an appreciable amount of zinc phosphate was detected in the PM2.5 fraction. The insoluble zinc forms in both the fractions are identified as Zn-sorbed-ferrihydrite and zinc sulphide. The variation of Zn speciation across different size fractions has implication on the bioavailability and toxicity of Zn. Such source specific speciation data are needed for developing source inventories, and for amending existing regulations/framing new regulations for different size fractions.

Effects of long-term paddy rice cultivation on soil arsenic speciation

Geochemical behavior of arsenic (As) in rice paddy soils determines the availability and mobility of As in the soils, but little is known about the long-term effects of paddy rice cultivation on As speciation in the soils. In this study, surface soil samples were collected from a rice paddy land and its adjacent dry land with similar soil properties and known cultivation histories. The soils of the paddy land and dry land contained 378 and 423 mg As kg−1, respectively. The predominant As species in the soils were investigated using As K-edge X-ray absorption spectroscopy (XAS) in combination with two sequential chemical fractionation methods. The XAS results showed that the predominant As species in the soils were As(III)- and As(V)-ferrihydrite, As(V)-goethite and scorodite. In comparison to the dry land soil, the paddy land soil contained a higher proportion of As(V)-ferrihydrite and a lower proportion of scorodite. The results of chemical fractionation revealed that As in the paddy land soil was more labile than that in the dry land soil. It is therefore suggested that long-term rice cultivation enhances the mobility and availability of As in paddy soils.

Photon-Induced, Timescale, and Electrode Effects Critical for the in Situ X-ray Spectroscopic Analysis of Electrocatalysts: The Water Oxidation Case

In situ experiments combining X-ray absorption spectroscopy (XAS) and electrochemistry have now become an indispensable tool for understanding the mechanisms of operation, structure, and the modes of degradation of electrocatalysts under operational conditions. Herein, the design of a gas- and liquid-tight spectroelectrochemical cell (SEC) and an experimental protocol for the simultaneous collection of high-quality XAS and electrochemical data are introduced. The effects of the working electrode, loading of active material, and X-ray damage are demonstrated and interpreted by an example of a well-known heterogenite-like cobalt oxide water oxidation catalyst. The SEC permitted reproducible X-ray absorption near edge structure to be collected with a resolution of at least 0.05 eV (equivalent to approximately 0.02 unit oxidation state sensitivity) and allowed X-ray-mediated photoeffects to be examined in detail. Furthermore, tracking of the potential-dependent changes in the oxidation state of a cobalt oxide catalyst with high precision and reproducibility is demonstrated. These in situ XAS data are correlated with a previous detailed electrokinetic analysis to identify the nature of the active state of the heterogenite-like water oxidation catalyst and conclude that metal oxidation states higher than IV are not involved in the catalytic mechanism. Finally, the implications of the significantly different timescales of the probed electron transfer events and the XAS analysis on the interpretation of the in situ spectroelectrochemical data are critically discussed, focusing on the mechanism of the water oxidation reaction.

Unraveling the Role of Al Substitution in Anionic Oxygen Activity of Ni-Rich Layered Oxide Cathodes

Ni-based layered oxides have attracted great attention for the development of high energy and high capacity Li-ion cathodes. The most popular Ni-based cathodes, LiNi x Mn y Co1-x-y O2 (NMC) and LiNi x Co y Al1-x-y O2 (NMC), are indeed derivatives of LiNiO2 by partially substituting Ni with Co, Mn or Al. The current trend to develop high-Ni and low-Co or Co-free layered Ni-based oxide cathodes, makes a strong push to the limit of Ni content in such layered oxides, leading to many common properties with their parent compound, LiNiO2. In fact, lithium nickel oxide often exists off-stoichiometry because of the presence of Ni2+ in the Li layer, which blocks the Li+ diffusion pathway upon lithiation/delithiation. Therefore, a second metal of a minimal content, such as Co or Al, which can somehow facilitate the formation of layered structure is still needed, although they are not strongly favored due to cost and sacrifice upon the use of inactive Al. In this work, a number of Al substituted lithium nickel oxides, LiAl x Ni1-x O2 (0 ≤ x ≤ 0.20), have been synthesized via a solid state reaction, showing good R m layered structure. Along with their parent LiNiO2, the oxygen activity in these compounds have been studied using combined synchrotron X-ray absorption spectroscopy (XAS), resonant inelastic X-ray scattering (RIXS) and differential electrochemical mass spectrometry (DEMS). The goal of this research is to elucidate the role of Al on the anionic oxygen activity in Ni-based layered oxides, including both reversible anionic oxygen redox and irreversible oxygen release during the electrochemical process. The electronic structure of transition metal and O was investigated at different states of charge to obtain a complete picture of cationic and anionic redox during the charge/discharge process. Beyond the redox chemistry, the effect of Al substitution on the phase transformation at highly delithiated states, dominated by H2 to H3 phase transformation for LiNiO2, as well as thermal stability was carefully studied. We hope this work helps provide a comprehensive picture of the role of Al substitution on the overall performance of Ni-based layered oxide cathodes.

A XAFS investigation of amorphous-to-crystalline and fluorite-to-pyrochlore phase transitions in Ln2M2O7 (Ln = Gd, Tb, Dy; M = Ti, Zr)

Amorphous-to-crystalline and fluorite-to-pyrochlore phase transitions in complex oxides Ln2M2O7 (Ln = Gd, Tb, Dy; M = Ti, Zr) prepared by sol-gel and coprecipitation methods were studied using x-ray absorption spectroscopy in combination with x-ray diffraction and Raman spectroscopy. The Ln titanates crystallize directly from the amorphous state to the pyrochlore structure, while the Ln zirconates form the intermediate fluorite phase first. We have found that both XANES and EXAFS data reflect the considerable difference between the crystallization processes of Ln titanates and zirconates. In particular the evolution of the K–Ti pre-edge features is a good indicator of the phase transition from amorphous to crystalline state. The splitting of the first Ln-O shell in the FT modulus of L3-Ln edge EXAFS spectra in Ln titanates can be regarded as a fingerprint of the ordered pyrochlore structure formation which is accompanied also by specific changes in the main features of the XANES spectra. For the Ln zirconates these features are less pronounced.

Structural Evolution and Dynamics of an In2O3 Catalyst for CO2 Hydrogenation to Methanol: An Operando XAS-XRD and In Situ TEM Study.

We report an operando examination of a model nanocrystalline In2O3 catalyst for methanol synthesis via CO2 hydrogenation (300 °C, 20 bar) by combining X-ray absorption spectroscopy (XAS), X-ray powder diffraction (XRD), and in situ transmission electron microscopy (TEM). Three distinct catalytic regimes are identified during CO2 hydrogenation: activation, stable performance, and deactivation. The structural evolution of In2O3 nanoparticles (NPs) with time on stream (TOS) followed by XANES-EXAFS-XRD associates the activation stage with a minor decrease of the In-O coordination number and a partial reduction of In2O3 due to the formation of oxygen vacancy sites (i.e., In2O3-x). As the reaction proceeds, a reductive amorphization of In2O3 NPs takes place, characterized by decreasing In-O and In-In coordination numbers and intensities of the In2O3 Bragg peaks. A multivariate analysis of the XANES data confirms the formation of In2O3-x and, with TOS, metallic In. Notably, the appearance of molten In0 coincides with the onset of catalyst deactivation. This phase transition is also visualized by in situ TEM, acquired under reactive conditions at 800 mbar pressure. In situ TEM revealed an electron beam assisted transformation of In2O3 nanoparticles into a dynamic structure in which crystalline and amorphous phases coexist and continuously interconvert. The regeneration of the deactivated In0/In2O3-x catalyst by reoxidation was critically assessed revealing that the spent catalyst can be reoxidized only partially in a CO2 atmosphere or air yielding an average crystallite size of the resultant In2O3 that is approximately an order of magnitude larger than the initial one.

Synchrotron Radiation Research and Analysis of the Particulate Matter in Deep Ice Cores: An Overview of the Technical Challenges

Airborne dust extracted from deep ice core perforations can provide chemical and mineralogical insight into the history of the climate and atmospheric conditions, with unrivalled temporal resolution, time span and richness of information. The availability of material for research and the natural complexity of the particulate, however, pose significant challenges to analytical methods. We present the developments undertaken to optimize the experimental techniques, materials and protocols for synchrotron radiation-based analysis, in particular for the acquisition of combined Synchrotron Radiation X-Ray Fluorescence and X-ray Absorption Spectroscopy data.

Characterization of Structural Iron in Smectites - An Ab Initio Based X-ray Absorption Spectroscopy Study.

Fe-bearing clay minerals are abundant in argillaceous rocks as their redox-active structural iron may control the sorption mechanism of redox sensitive elements on the surface of clay minerals. The extent and efficiency of the redox reactions depend on the oxidation state (Fe2+/Fe3+ ratio) and structural distribution of the substituting cations in the TOT-layer of clay minerals. Even smectites with similar structure originating from different locations might have a distinct arrangement of isomorphic substitutions (e.g., individual iron or Fe-Fe pairs). In this study, the proportion of different iron distribution in Milos-, Wyoming-, and Texas-montmorillonite was determined by combining X-ray absorption spectroscopy (XAS) with ab initio calculations. The relaxed atomic structures of the smectite models with different arrangement of individual Fe atoms and Fe-Fe/Fe-Mg clusters served as the basis for the calculations of the XAS spectra. The combination of simulation results and measured Fe K-edge XAS spectra of Wyoming-, Milos- and Texas-montmorillonites suggested that iron is present as Fe3+ in the octahedral sheet. Fe3+ in Texas-montmorillonite has a tendency to form clusters, while no definitive statement about clustering or avoidance of Fe-Fe and Fe-Mg pairs can be made for Milos- and Wyoming-montmorillonite.

Highly dispersed PdS preferably anchored on In2S3 of MnS/In2S3 composite for effective and stable hydrogen production from H2S

As an important byproduct during natural gas exploitation, green utilization of hydrogen sulfide (H2S) by photocatalysis has offered us the possibility for production of clean hydrogen (H2) from H2S with low energy consumption. In this work, we have successfully introduced well-dispersed palladium sulfide (PdS) which is preferably loaded on In2S3 of MnS/In2S3 composite for improved photocatalytic hydrogen evolution from H2S aqueous solution. In contrast to binary MnS/In2S3, ternary MnS/In2S3/PdS has exhibited a remarkable and stable hydrogen production rate of 22.7 mmol g−1 h−1 with an apparent quantum yield of 34% at around 395 nm. A comprehensive structure characterization of the ternary composite including scanning transmission electron microscopy (STEM) and X-ray absorption spectroscopy (XAS) in combination with theoretical calculations confirm the good dispersion of PdS in the composite. Moreover, we discovered that PdS preferably interact with In2S3 rather than MnS in the composite through Pd-S-In bond on the interface of the two. Photoluminescence (PL) spectra, surface photovoltage (SPV) spectra together with transient photocurrent and electrochemical impedance spectra (EIS) demonstrate the advantage of PdS for promoting the charge separation. This work sheds light on the positive effect on the enhanced activity of the corresponding system resulting from the preferable anchoring of highly dispersed PdS on In2S3 in the composite by chemical Pd-S-In bond. Not only the high dispersion but also the preferable anchoring of the co-catalyst in the composite could hence inspire people for more rational designs of ternary composite in future.

Electronic localization in CaVO3 films via bandwidth control

Understanding and controlling the electronic structure of thin layers of quantum materials is a crucial first step towards designing heterostructures where new phases and phenomena, including the metal-insulator transition (MIT), emerge. Here, we demonstrate control of the MIT via tuning electronic bandwidth and local site environment through selection of the number of atomic layers deposited. We take CaVO3, a correlated metal in its bulk form that has only a single electron in its V4+ 3d manifold, as a representative example. We find that thick films and ultrathin films (≤6 unit cells, u.c.) are metallic and insulating, respectively, while a 10 u.c. CaVO3 film exhibits a clear thermal MIT. Our combined X-ray absorption spectroscopy and resonant inelastic X-ray scattering (RIXS) study reveals that the thickness-induced MIT is triggered by electronic bandwidth reduction and local moment formation from V3+ ions, that are both a consequence of the thickness confinement. The thermal MIT in our 10 u.c. CaVO3 film exhibits similar changes in the RIXS response to that of the thickness-induced MIT in terms of reduction of bandwidth and V 3d–O 2p hybridization.

Carbon-supported Pt during aqueous phenol hydrogenation with and without applied electrical potential: X-ray absorption and theoretical studies of structure and adsorbates

Adsorbed hydrogen and phenol on Pt nanoparticles during (electro)catalytic hydrogenation are explored by combining X-ray absorption spectroscopy and ab initio simulations. Direct evidence for two types of Pt-C bonds at the surface of the metal particles detected by X-ray absorption spectroscopy suggest strong bonding between metal and the carbon support as well as adsorption of phenol nearly parallel to the surface. Hydrogen and phenol compete for accessible Pt sites. The surface concentrations are compatible with the proposal that atomic hydrogen and chemisorbed phenol are the species reacting in the rate-determining step of hydrogenation in the presence and absence of an external cathodic potential. During electrocatalytic hydrogenation the external electric potential controls the concentration of species on the surface, but does not impose structural or electronic property changes of the Pt compared to Pt particles in presence of hydrogen gas. Increasing reaction rates with increasing cathodic potential are attributed to the increase in chemical potential of adsorbed H.

Strain-Induced Stabilization of Charged State in Li-Rich Layered Transition-Metal Oxide for Lithium-Ion Batteries

Li-rich layered oxide (LLO) is a promising cathode material for lithium-ion batteries because of its large capacity in comparison with conventional layered rock-salt structure materials. In contrast to the conventional materials, it is known that LLO of 3d transition metal has a nanodomain microstructure; however, roles of each domain and effects of strain, induced by the microstructure, on electrode properties are still unclear. In this study, the influence of the strain on an electronic structure is studied to elucidate the stabilization mechanism of LLO material Li[Li0.2Ni0.2Mn0.6]O2 in the charged state by using resonant X-ray diffraction spectroscopy (RXDS), X-ray diffraction, and X-ray absorption spectroscopy (XAS) in combination with ab initio calculation. RXDS of a superlattice peak and XAS at Mn and Ni K-edges unveil that this material has a microstructure consisting of Mn-rich and Ni-rich domains, whose structures are similar to Li2MnO3 and LiNiO2, respectively. In the Ni-rich domain, trigonal d...

Extracting the Americyl Hydration from an Americium Cationic Mixture in Solution: A Combined X-ray Absorption Spectroscopy and Molecular Dynamics Study.

Am(VI) solution chemistry differs from that of lighter actinoids, as U, Pu, and Np, where the actinyl [AnO2]2+ is the most stable form and plays an important role in nuclear fuel technology. The behavior of americium in solution shows the trend to stabilize lower oxidation states, mainly Am(III). Riddle and co-workers recently reported the EXAFS and first XANES spectra of an americium-containing aqueous solution where the americyl species is detected in a mixture. We have developed Am3+-H2O and [AmO2]2+-H2O intermolecular potentials based on quantum-mechanical calculations to carry out classical MD simulations of these two cations in water. Structural information extracted from the statistical trajectories has been used to simulate EXAFS and XANES spectra of both solutions. For the Am3+ case the theoretical-experimental agreement for both EXAFS and XANES spectra is satisfactory. This is not the case for the [AmO2]2+ aqueous solutions. However, when an aqueous solution mixture of both cationic forms in a 55/45 [AmO2]2+/Am3+ ratio is considered, the theoretical-experimental agreement is recovered. EXAFS and XANES spectra which would correspond to a pure [AmO2]2+ aqueous solution are proposed. In the XANES case, the main features characterizing the simulated spectrum are consistent with those previously found in the experimental XANES spectra of stable [UO2]2+ and [PuO2]2+ in water.