Mo K-edge Research Articles

The influence of Zn2+ ions on the local structure and thermochromic properties of Cu1-xZnxMoO4 solid solutions

The influence of zinc ions on the thermochromic properties of polycrystalline Cu1−xZnxMoO4 (x=0.10, 0.50, 0.90) solid solutions was studied by X-ray absorption spectroscopy at the Cu, Zn and Mo K-edges. Detailed structural information on the local environment of metal ions was obtained from the simultaneous analysis of EXAFS spectra measured at three metal absorption edges using the reverse Monte Carlo method. Thermochromic phase transition with the hysteretic behaviour between α and γ phases was observed in Cu0.90Zn0.10MoO4 solid solution. It was found that the local environment of molybdenum ions is most susceptible to the substitution of copper for zinc and, upon cooling, transforms from tetrahedral MoO4 to distorted octahedral MoO6.

In-Situ X-Ray Absorption Spectroscopy Study of Electrocatalytic Reduction of Carbon Dioxide with Molybdenum Disulfide

Electrocatalytic reactions offer alternative routes for the conversion and storage of energy. For instance, the electrocatalytic reduction of carbon dioxide could lead to energy-rich syngas, methanol, or even hydrocarbons. Layered transition metal dichalcogenide nanomaterials, such as MoS2, have emerged as electrocatalysts towards CO2 reduction with high efficiency and low overpotentials. However, the underlying chemical and electronic states defining the catalytic activity have not yet been completely defined. These key states can be probed for both metals and ligands in selected MX2 (M=W, Mo; X=S, Se) using synchrotron-based X-ray absorption spectroscopy (XAS). In recent work we performed in-situ XAS measurements at Mo K-edge and S K-edge for MoS2 nanosheets. Measurements at the S K-edge showed drastic changes at the pre-edge and edge indicating changes in number of available unoccupied states and Zeff respectively. On the other hand, only a small shift of the Mo K-edge was observed. Metal d-states are found to be the active site for catalysis, yet the ligand K-edge presents a better method to examine catalytic processes. Since the pre-edge reflects a transition to metal-ligand hybridized states, its intensity and position gives direct insight into the activity and changes of d-states. Given the vast compositional space of metal and ligand for MX2, the knowledge of how d-state activity will serve to pave the way to a better study of metal and chalcogenide combinations to improve the electrocatalytic performance. Figure 1

Controlling MoO2 and MoO3 phases in MoOx/CNTs nanocomposites and their application to anode materials for lithium-ion batteries and capacitors

Molybdenum oxides (MoO2 and MoO3) are attractive anode materials for Li- and Na- ion batteries. Although there have been extensive studies on them individually, systematic and comparative studies are still lacking. In this work, we demonstrate a facile and straightforward synthesis method to control the phase and oxidation state in the MoOx/CNTs nanocomposites via hydrothermal reaction followed by heat-treatment. By changing the gas atmosphere during the annealing process, well-dispersed MoO2/CNTs and MoO3/CNTs nanocomposites are formed without altering their overall morphology. This strategy enables us to investigate the true structure-property correlation of MoOx/CNTs nanocomposites by comparing the structure and electrochemical properties of MoO2/CNTs and MoO3/CNTs. When tested as anode materials for lithium-ion batteries, both HT-MoO2&3/CNTs electrodes show much-improved cycling stability and rate performance compared to the rod-shaped bulk MoO3 electrode. In situ Mo K-edge x-ray absorption spectroscopy (XAS) has been further employed to compare and elucidate Li+ storage mechanisms of both electrodes. When employed to the negative electrode of a high-power lithium-ion capacitor (LIC), the LIC full-cell composed of HT-MoO3/CNTs negative and activated carbon positive electrodes demonstrates impressive energy and power densities (~ 90 Wh kg−1 with 2000 W kg−1) and excellent cycling stability (96.8 % capacity retention after 300 cycles), revealing the versatility of the MoOx/CNTs electrodes in energy applications.

INCORPORATION OF Mo6+ IN FERRIHYDRITE, GOETHITE, AND HEMATITE

Among all iron oxides, hematite (α-Fe2O3), goethite (α-FeOOH), and ferrihydrite (FeOOH⋅nH2O) are the most common mineral species. While immobilization of Mo6+ by surface adsorption on ferric oxides has been studied extensively, the mechanisms of incorporation in their structure have been researched little. The objective of this study was to investigate the relation between Mo content and its structural incorporation in hematite, goethite, and six-line ferrihydrite by a combination of X-ray absorption spectroscopy (XAS), powder X-ray diffraction (pXRD), and inductively-coupled plasma optical emission spectrometry (ICP-OES). Synthesized in the presence of Mo, the hematite, goethite, and six-line ferrihydrite phases incorporated up to 8.52, 0.03, and 17.49 wt. % Mo, respectively. For hematite and goethite, pXRD analyses did not indicate the presence of separate Mo phases. Refined unit-cell parameters correlated with increasing Mo concentration in hematite and goethite. The unit-cell parameters indicated an increase in structural disorder within both phases and, therefore, supported the structural incorporation of Mo in hematite and goethite. Analysis of pXRD measurements of Mo-bearing six-line ferrihydrites revealed small amounts of coprecipitated akaganéite. X-ray absorption near edge structure (XANES) measurements at the Mo L3-edge indicated a strong distortion of the MoO6 octahedra in all three phases. Fitting of extended X-ray absorption fine structure (EXAFS) spectra of the Mo K-edge supported the presence of such distorted octahedra in a coordination environment similar to the Fe position in the investigated specimen. Incorporation of Mo6+ at the Fe3+-position for both hematite and goethite resulted in the formation of one Fe vacancy in close proximity to the newly incorporated Mo6+ and, therefore, charge balance within the hematite and goethite structures.

Local disorder and structure relation induced by magnetic exchange interactions in A2(Mo1−yMny)2O7 pyrochlores

We present an extended X-ray absorption fine structure study at the Mo K-edge of A2(Mo1−yMny)2O7 (A = Gd, Ho; y = 0.05 and 0.10) pyrochlores, as a function of temperature and composition, coupled to diffractometric and magnetic characterizations. Extending the study reported in our previous paper on the pristine A2Mo2O7 compounds to these Mo/Mn partially substituted samples, where we hypothesize a competition between double-exchange and superexchange couplings, we aim to check which structure parameters are related to the nature of the nearest-neighbor magnetic interactions, looking for the presence and evolution of order and structure anomalies. Two Ho samples Ho2(Mo1−yMny)2O7 (y = 0.05 and 0.10) keep the spin-glass nature of the parent compositions with a strong distortion of the MoO(1)6 octahedron and of the Mo‒Ho and Mo‒Mo second shell. On the other hand, two Gd2(Mo1−yMny)2O7 samples, ferromagnetic at low temperature in the undoped case, show the appearance on a local scale of a spin-glass transition mirrored by a quite high structure disorder and by a distortion coherent with a lattice frustration after Mn-doping. Therefore, the Gd and Ho Mn-doped samples display a similar frustrated behavior, differently from the corresponding undoped ones.

Experimental studies and thermodynamic assessment of the Ba-Mo-O system by the CALPHAD method

Thermodynamic measurements on BaMoO4, BaMoO3 and BaMo3O10 are reported, that served as input for the development of a thermodynamic model of the Ba-Mo-O system using the CALPHAD methodology. The valence states of molybdenum in BaMoO4 and BaMoO3 were confirmed to be VI and IV, respectively, from X-ray Absorption Near Edge Structure Spectroscopy measurements at the Mo K-edge. The heat capacity at low temperatures of these compounds was obtained from thermal-relaxation calorimetry. Phase equilibrium data in the BaMoO4-MoO3 section were also measured, and the transition enthalpy associated with the peritectic decomposition of BaMo3O10 was determined using Differential Scanning Calorimetry. The developed thermodynamic model used the compound energy formalism for intermediate compounds, and an ionic two-sublattice model for the liquid phase. The optimized Gibbs energies were assessed with respect to the known thermodynamic and phase equilibrium data. A good agreement is generally obtained, but a number of ill-defined data were also identified.

Sorption and speciation of molybdate in soils: Implications for molybdenum mobility and availability

Molybdenum (Mo) is an emerging contaminant in the environment. To assess the mobility and availability of Mo in soils, this study investigated the effect of soil properties on the sorption and desorption of Mo in soils. The Mo K-edge X-ray absorption near edge structure (XANES) of the soils after Mo sorption showed that sorbed molybdate was the predominant species, with Fe/Al-molybdate and Ca-molybdate being the minor components in soils with low and high pH levels, respectively. Although acidic soils exhibited higher Mo sorptivity, they exhibited partial reversibility of Mo sorption, which may be attributed to the high solubility of Al-molybdate. Accordingly, the mobility of Mo may be relatively high in soils with a low pH, high exchangeable Al content, and high Fe-hydroxide crystallinity, such as Ultisols and Oxisols. At higher pHs, the sorption irreversibility of molybdate were enhanced due to the formation of Ca-molybdate precipitate. The results of this study indicated that sorption/desorption irreversibility and related mechanisms should be considered when evaluating the mobility and availability of Mo in soils.

Preparation and spectroscopic characterization of lyophilized Mo nitrogenase

Mo nitrogenase is the primary source of biologically fixed nitrogen, making this system highly interesting for developing new, energy efficient ways of ammonia production. Although heavily investigated, studies of the active site of this enzyme have generally been limited to spectroscopic methods that are compatible with the presence of water and relatively low protein concentrations. One method of overcoming this limitation is through lyophilization, which allows for measurements to be performed on solvent free, high concentration samples. This method also has the potential for allowing efficient protein storage and solvent exchange. To investigate the viability of this preparatory method with Mo nitrogenase, we employ a combination of electron paramagnetic resonance, Mo and Fe K-edge X-ray absorption spectroscopy, and acetylene reduction assays. Our results show that while some small distortions in the metallocofactors occur, oxidation and spin states are maintained through the lyophilization process and that reconstitution of either lyophilized protein component into buffer restores acetylene reducing activity.Graphic abstract

Coordination Number Regulation of Molybdenum Single-Atom Nanozyme Peroxidase-like Specificity

Summary Nanozymes are promising alternatives to natural enzymes, but their use remains limited owing to poor specificity. Overcoming this and controlling the targeted enzyme-like performance of traditional nanozymes is extremely challenging due to the intrinsic structural complexity of these systems. We report theoretical design and experimental realization of a series of heterogeneous molybdenum single-atom nanozymes (named MoSA–Nx–C), wherein we find that the peroxidase-like specificity is well regulated by the coordination numbers of single Mo sites. The resulting MoSA–N3–C catalyst shows exclusive peroxidase-like behavior. It achieves this behavior via a homolytic pathway, whereas MoSA–N2–C and MoSA–N4–C catalysts have a different heterolytic pathway. The mechanism of this coordination-number-dependent enzymatic specificity is attributed to geometrical structure differences and orientation relationships of the frontier molecular orbitals toward these MoSA–Nx–C peroxidase mimics. This study demonstrates the rational design of peroxidase-specific nanozymes and precise regulation of their enzymatic properties.

Characterization of a Mo-Nitrogenase Variant Containing a Citrate-Substituted Cofactor.

Nitrogenase converts N2 to NH3 , and CO to hydrocarbons, at its cofactor site. Herein, we report a biochemical and spectroscopic characterization of a Mo-nitrogenase variant expressed in an Azotobacter vinelandii strain containing a deletion of nifV, the gene encoding the homocitrate synthase. Designated NifDKCit , the catalytic component of this Mo-nitrogenase variant contains a citrate-substituted cofactor analogue. Activity analysis of NifDKCit reveals a shift of CO reduction from H2 evolution toward hydrocarbon formation and an opposite shift of N2 reduction from NH3 formation toward H2 evolution. Consistent with a shift in the Mo K-edge energy of NifDKCit relative to that of its wild-type counterpart, EPR analysis demonstrates a broadening of the line-shape and a decrease in the intensity of the cofactor-originated S=3/2 signal, suggesting a change in the spin properties of the cofactor upon citrate substitution. These observations point to a crucial role of homocitrate in substrate reduction by nitrogenase and the possibility to tune product profiles of nitrogenase reactions via organic ligand substitution.

Synthesis, cathode property and crystal, electronic and local structures of Mg2Mo3O8 as Mg rechargeable battery cathode material

Mg2Mo3O8 was synthesized by a solid-phase method in a high vacuum atmosphere. According to the combination of ICP-AES technique and Rietveld analysis for synchrotron X-ray and neutron diffraction patterns, the structure and composition of the synthesized material was identified as single phase of the layered Mg2Mo3O8 of P63mc space-group. Charge and discharge cycle tests showed that Mg2Mo3O8 with carbon composite exhibited 18 and 89 mAh g−1 of initial charge and discharge capacities at 90 °C. Reversible charge/discharge behavior was confirmed up to 5 cycles. Electrochemical demagnesiation using Li anode showed deintercalation of 0.45 Mg2+ pfu. The valence of the Mo in synthesized material was determined by XAFS, whose spectrum at the Mo K-edge confirmed the reductive synthesis of Mg2Mo3O8 because of not hexavalent but reduced tetravalent Mo. Since the Mo K-edge XANES spectrum after first charge was oxidized from tetravalent, it was revealed that the Mg2Mo3O8 could electrochemically demagnesiate in the present cell-condition using [Mg(G4)][TFSA]2/[PYR13][TFSA] electrolyte. The PDF data from synchrotron X-ray total scattering was used to analyze the local structure. The local structure leads to the Mg hopping route in Mg2Mo3O8, where tetrahedrally coordinated Mg hops via octahedral site.

Structural and Thermodynamic Investigation of the Perovskite Ba2NaMoO5.5.

Neutron diffraction, X-ray absorption spectroscopy (XAS), and Raman spectroscopy measurements of the quaternary perovskite phase Ba2NaMoO5.5 have been performed in this work. The cubic crystal structure in space group Fm3̅m has been refined using the Rietveld method. X-ray absorption near-edge structure spectroscopy (XANES) measurements at the Mo K-edge have confirmed the hexavalent state of molybdenum. The local structure of the molybdenum octahedra has been studied in detail using extended X-ray absorption fine structure (EXAFS) spectroscopy. The Mo–O and Mo–Ba distances have been compared to the neutron diffraction data with good agreement. The coefficient of thermal expansion measured in the temperature range of 303–923 K, using high temperature X-ray diffraction (HT-XRD) (αV = 55.8 × 10–6 K), has been determined to be ∼2 times higher than that of the barium molybdates BaMoO3 and BaMoO4. Moreover, no phase transition nor melting have been observed, neither by HT-XRD nor Raman spectroscopy nor differential scanning calorimetry, up to 1473 K. Furthermore, the standard enthalpy of formation (ΔfHm°) for Ba2NaMoO5.5(cr) has been determined to be −(2524.75 ± 4.15) kJ mol−1 at 298.15 K, using solution calorimetry. Finally, the margin for safe operation of sodium-cooled fast reactors (SFRs) has been assessed by calculating the threshold oxygen potential needed, in liquid sodium, to form the quaternary compound, following an interaction between irradiated mixed oxide (U,Pu)O2 fuel and sodium coolant.

Anion Binding and Oxidative Modification at the Molybdenum Cofactor of Formate Dehydrogenase from Rhodobacter capsulatus Studied by X-ray Absorption Spectroscopy.

Formate dehydrogenase (FDH) enzymes are versatile catalysts for CO2 conversion. The FDH from Rhodobacter capsulatus contains a molybdenum cofactor with the dithiolene functions of two pyranopterin guanine dinucleotide molecules, a conserved cysteine, and a sulfido group bound at Mo(VI). In this study, we focused on metal oxidation state and coordination changes in response to exposure to O2, inhibitory anions, and redox agents using X-ray absorption spectroscopy (XAS) at the Mo K-edge. Differences in the oxidative modification of the bis-molybdopterin guanine dinucleotide (bis-MGD) cofactor relative to samples prepared aerobically without inhibitor, such as variations in the relative numbers of sulfido (Mo═S) and oxo (Mo═O) bonds, were observed in the presence of azide (N3-) or cyanate (OCN-). Azide provided best protection against O2, resulting in a quantitatively sulfurated cofactor with a displaced cysteine ligand and optimized formate oxidation activity. Replacement of the cysteine ligand by a formate (HCO2-) ligand at the molybdenum in active enzyme is compatible with our XAS data. Cyanide (CN-) inactivated the enzyme by replacing the sulfido ligand at Mo(VI) with an oxo ligand. Evidence that the sulfido group may become protonated upon molybdenum reduction was obtained. Our results emphasize the role of coordination flexibility at the molybdenum center during inhibitory and catalytic processes of FDH enzymes.

Investigation of the Reducibility of Supported Oxomolybdate Species for Mapping of Active Centers of Partial Oxidation Reaction: In Situ Mo K-Edge XAS and DFT Study

We have investigated the molecular and electronic structure of a TiO2-supported oxomolybdate phase upon reduction under methanol or dihydrogen atmosphere. In situ Mo K-edge X-ray absorption spectro...

High-temperature X-ray absorption spectroscopy study of thermochromic copper molybdate

X-ray absorption spectroscopy at the Cu and Mo K-edges was used to study the effect of heating on the local atomic structure and dynamics in copper molybdate (α-CuMoO4) in the temperature range from 296 to 973 K. The reverse Monte-Carlo (RMC) method was successfully employed to perform accurate simulations of EXAFS spectra at both absorption edges simultaneously. The method allowed us to determine structural models of α-CuMoO4 being consistent with the experimental EXAFS data. These models were further used to follow temperature dependencies of the local environment of copper and molybdenum atoms and to obtain the mean-square relative displacements for Cu–O and Mo–O atom pairs. Moreover, the same models were able to interpret strong temperature-dependence of the Cu K-edge XANES spectra. We found that the local environment of copper atoms is more affected by thermal disorder than that of molybdenum atoms. While the MoO4 tetrahedra behave mostly as the rigid units, a reduction of correlation in atomic motion between copper and axial oxygen atoms occurs upon heating. This dynamic effect seems to be the main responsible for the temperature-induced changes in the O2−→Cu2+ charge transfer processes and, thus, is the origin of the thermochromic properties of α-CuMoO4 upon heating above room temperature.

Highly dispersed molybdenum containing mesoporous silicate (Mo-TUD-1) for olefin metathesis

Abstract Employing a one-pot sol-gel synthesis technique, molybdenum with variable loadings (2–14 wt%), was successfully incorporated into a mesoporous TUD-1 silicate framework. Diffuse reflectance UV–vis and Raman spectra of samples dehydrated at reaction temperatures (450 °C) revealed the dominant presence of highly dispersed tetrahedral di-oxo (Si-O)2Mo(=O)2 species. Neither bulk nor crystalline MoO3 was evident at Mo loadings from 2 to 7 wt.% from complementary analytical techniques suggesting that a high dispersion of MoOx species is achieved by this synthesis method. Mo L-edge XANES of catalyst samples at ambient conditions and Mo K-edge XAS of catalyst samples dehydrated at the reaction temperature (450 °C) further confirm the existence of mixed tetrahedral and octahedral Mo sites. The relative population of dioxo Mo species observed in Mo-TUD-1 catalysts at various Mo loadings correlate well with the Lewis acidity and apparent TOFs (mmol propene/mol Mo/s) observed with these samples. These observations confirm that the dioxo Mo species are the active site precursors, as also reported previously with other Mo-based catalyst formulations. Compared to Mo-impregnated SiO2 (Mo/SiO2) catalyst, the Mo-TUD-1 catalysts (2–7 wt% Mo loadings) provide higher apparent TOFs. At higher Mo loadings, the fraction of MoO3 species that are Bronsted acidic in nature increases, resulting in decreased TOFs and increased catalyst deactivation due to the formation of heavier hydrocarbons that deposit on the catalyst surface. However, the metathesis activity is fully restored after simple air regeneration of the catalyst.

Anharmonicity in elastic constants and extended x-ray-absorption fine structure cumulants

We have investigated temperature dependence of the elastic constants and higher-order EXAFS (extended x-ray-absorption fine structure) cumulant moments, both of which originate from vibrational anharmonicity. We focus our attention on how the third- or fourth-order anharmonicity contributes to these physical quantities. Although it may be believed that the fourth-order anharmonicity should dominantly contribute to the fourth-order EXAFS cumulant through the first-order quantum statistical perturbation theory, it is consequently found that the experimental fourth-order EXAFS cumulant observed in fcc Ni, Cu, and stainless steel 316 are described mainly by the third-order anharmonicity through the second-order perturbation. In case of the elastic constants, such a situation is more prominent, and the contribution of the fourth-order anharmonicity is negligibly small for the estimation of temperature dependence of the elastic constants. We have also observed significant lattice strains on Cr and Mo in stainless steel 316 through the Fe, Ni, Cr, and Mo K-edge EXAFS measurements: a compressive lattice strain on Cr associated with larger thermal fluctuations and a more significant compressive lattice strain on Mo without enhanced thermal fluctuation. Such a characteristic dissimilarity may be caused by the differences in the atomic weights and the cohesive energies between Cr and Mo. Moreover, we have performed path-integral effective classical potential and classical Monte-Carlo simulations to describe the bulk moduli of the Invar and Elinvar alloys that show noticeable anomalies due to the so-called Invar effect. Appropriate temperature dependence of the bulk moduli is successfully obtained for the Invar, Elinvar, and stainless steel 304 and 316 alloys as well as elemental fcc Cu and Ni metals.

Ultrafine Metallic Nickel Domains and Reduced Molybdenum States Improve Oxygen Evolution Reaction of NiFeMo Electrocatalysts.

An electrocatalyst for oxygen evolution reaction (OER) is essential in the realization of renewable energy conversion technologies, but its large overpotential, slow charge transfer, and degradation of surface reaction sites are yet to be overcome. Here, it is found that the metallic nickel domains and high-valence reduced molybdenum ions of NiFeMo electrocatalysts grown on a 3D conductive and porous electrode without using binders enable ultrahigh performance in OER. High resolution-transmission electron microscope and extended X-ray absorption fine structure analyses show that metallic nickel domains with Ni-Ni bonds are generated on the catalyst surface via a dry synthesis using nitrogen plasma. Also, Mo K-edge X-ray absorption near-edge spectroscopy reveals that Mo6+ ions are reduced into high-valence modulating Mo4+ ions. With the metallic nickel domains facilitating the adsorption of oxygen intermediates to low-coordinated Ni0 and the Mo4+ pulling their electrons, the catalyst exhibits about 60-fold higher activity than a Mo-free NiFe catalyst, while giving about threefold faster charge transfer along with longer stability over 100 h and repeated 100 cycles compared to a bare NiFeMo catalyst. Additionally, these metallic domains and high-valence modulating metal ions are exhibited to give high Faradaic efficiency over 95%.

Pressure-induced structural changes in α-MoO3 probed by X-ray absorption spectroscopy

Energy-dispersive X-ray absorption spectroscopy at the Mo K-edge was used to study pressure-induced (up to 36 GPa) changes in the local atomic structure of 2D layered oxide α-MoO3. A linear combination analysis based on the low and high-pressure X-ray absorption near edge structure (XANES) spectra shows clear evidence of two high-pressure phases, existing at 18-25 GPa and above 32 GPa. The first transition is due to gradual decrease of the interlayer gap, whereas the second one – to its collapse and oxide structure reconstruction. The local atomic structure around molybdenum atoms at 0.2, 18.5 and 35.6 GPa was determined from the extended X-ray absorption fine structure (EXAFS) using reverse Monte Carlo calculations.

Resolving the structure of the E1 state of Mo nitrogenase through Mo and Fe K-edge EXAFS and QM/MM calculations.

Biological nitrogen fixation is predominately accomplished through Mo nitrogenase, which utilizes a complex MoFe7S9C catalytic cluster to reduce N2 to NH3. This cluster requires the accumulation of three to four reducing equivalents prior to binding N2; however, despite decades of research, the intermediate states formed prior to N2 binding are still poorly understood. Herein, we use Mo and Fe K-edge X-ray absorption spectroscopy and QM/MM calculations to investigate the nature of the E1 state, which is formed following the addition of the first reducing equivalent to Mo nitrogenase. By analyzing the extended X-ray absorption fine structure (EXAFS) region, we provide structural insight into the changes that occur in the metal clusters of the protein when forming the E1 state, and use these metrics to assess a variety of possible models of the E1 state. The combination of our experimental and theoretical results supports that formation of E1 involves an Fe-centered reduction combined with the protonation of a belt-sulfide of the cluster. Hence, these results provide critical experiment and computational insight into the mechanism of this important enzyme.