Structural and chemical state of doped and impregnated mesoporous Ni/CeO 2 catalysts for the water-gas shift
Abstract not provided
Vovchok, Dimitriy↗
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Chemical state of pre-solar matter
Consideration is given to several features of the chemical state of interstellar matter that may be relevant to the observed properties of chondrules if they are formed from aggregates of pre-existing particles. First, a brief summary of the numbers and types of interstellar particles as indicated by the extinction of starlight is given. Second, a model of the free decay interval required by the low solar abundance of 129-I is advanced. This model can support variations in the 129-I/127-I ratio that are larger than typical isotopic anomalies. Third, a new steady-state model of the chemical state of the interstellar medium is presented as a first step toward a quantitative distribution of the abundances among different chemical forms. Last, the advantages of fusing chondrules from aggregates of pre-solar dust by the action of exothermic chemistry are enumerated.
Clayton, D. D.↗
Deduction of the chemical state and the electronic structure of Nd{sub 2}Fe{sub 14}B compound from X-ray photoelectron spectroscopy core-level and valence-band spectra
Characterization of chemical state and electronic structure of the technologically important Nd{sub 2}Fe{sub 14}B compound is attractive for understanding the physical nature of its excellent magnetic properties. X-ray photoelectron spectroscopy (XPS) study of such rare-earth compound is important and also challenging due to the easy oxidation of surface and small photoelectron cross-sections of rare-earth 4f electrons and B 2p electrons, etc. Here, we reported an investigation based on XPS spectra of Nd{sub 2}Fe{sub 14}B compound as a function of Ar ion sputtering time. The chemical state of Fe and that of B in Nd{sub 2}Fe{sub 14}B compound can be clearly determined to be 0 and −3, respectively. The Nd in Nd{sub 2}Fe{sub 14}B compound is found to have the chemical state of close to +3 instead of +3 as compared with the Nd in Nd{sub 2}O{sub 3}. In addition, by comparing the valence-band spectrum of Nd{sub 2}Fe{sub 14}B compound to that of the pure Fe, the contributions from Nd, Fe, and B to the valence-band structure of Nd{sub 2}Fe{sub 14}B compound is made more clear. The B 2p states and B 2s states are identified to be at ∼11.2 eV and ∼24.6 eV, respectively, which is reported for the first time. The contribution from Nd 4f states can be identified both in XPS core-level spectrum and XPS valence-band spectrum. Although Nd 4f states partially hybridize with Fe 3d states, Nd 4f states are mainly localized in Nd{sub 2}Fe{sub 14}B compound.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Statistical White-Line Analysis in High-Throughput TXM-XANES for Chemical State Quantification
The transmission X-ray microscopy (TXM) based X-ray absorption near-edge structure (XANES) technique provides three-dimensional mapping of element-specific chemical states at nanometer-scale spatial resolution and micrometer-scale fields of view. However, compared to conventional volume-averaged XANES (VA-XANES) measurements, the inherently small voxel size in TXM-XANES leads to a lower signal-to-noise ratio, making full-spectrum analysis computationally demanding and less robust. Here, we present the structural and compositional conditions for a statistical white-line analysis framework under which chemical state information can be directly extracted from the white-line peak position in voxel spectra without the need for voxel-wise background subtraction or normalization, under well-defined structural and compositional conditions. The method is validated on layered oxide cathode materials, where low-order polynomial fitting accurately reproduces white-line features, and the extracted energy distributions correlate strongly with VA-XANES results. This statistical approach enables high-throughput, dose-efficient, and noise-robust chemical state quantification in TXM-XANES, offering broad applicability to functional materials requiring nanoscale oxidation-state mapping.
TXM↗
Green solid-state chemical synthesis and excellent xylene-detecting behaviors of Y-doped α-MoO{sub 3} nanoarrays
Graphical abstract: Y-doped α-MoO{sub 3} arrays constructed by nanorods are firstly synthesized by facile two-step solid-state chemical reaction, which exhibited excellent xylene-sensing property. - Highlights: • The Y-doped α-MoO{sub 3} nanoarrays constructed by nanorods were simply synthesized by solid-state chemical reaction. • The α-MoO{sub 3} arrays exhibited excellent gas-sensing properties for xylene. • This study is helpful to explore the xylene gas-sensitive materials with good comprehensive performance. - Abstract: Y-doped α-MoO{sub 3} nanoarrays constructed by nanorods were simply synthesized by a facile and simple two-step solid-state chemical reaction. X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy were applied to characterize the micro-structures and surface chemical composition of the as-prepared products. The results suggested that Y element had been successfully doped into the α-MoO{sub 3} nanoarrays. The gas-sensing behaviors of Y-doped nanoarrays toward seven kinds of harmful gases were also investigated. The results indicated that the Y-doped α-MoO{sub 3} nanoarrays display not only an improved response (the response value reaches 28.3 to 100 ppm xylene), but also an excellent selectivity to xylene. The good xylene-detecting behaviors were attributed to smaller size and the relative larger surface area. Furthermore, the doping of Y increased the electron donor defects and oxygen vacancies, which accelerated the mobility of oxygen ions and enhanced the conductivity of material, resulting in enhanced response to xylene.
36 MATERIALS SCIENCE↗
Chemical state of nickel nanoparticles during the oxygen evolution reaction in a carbonate-bicarbonate buffer solution
The chemical state of nickel anodes during the oxygen evolution reaction can impact their electrocatalytic performance. Here, X-ray photoelectron and absorption spectroscopies reveal the chemical state of nickel nanoparticles under oxygen evolution reaction conditions in amildly alkaline carbonate-bicarbonate buffer solution. Ni 2+ and Ni 3+ species are observed at the reaction onset potential with a 7:4 ratio, with no remaining metallic nickel. These species include NiO, which increasingly converts to other Ni 2+ and Ni 3+ species once the potential is increased above the onset potential. Conversely, when a 20-nm-thick nickel film is used instead of nickel nanoparticles, a significant amount of metallic nickel remains in the inner layers. Nickel nanoparticles also undergo significant morphological and structural changes during the reaction, as evidenced by ex situ transmission electron microscopy. Amorphization of the nanoparticles is attributed to significant H 2 O incorporation, with the oxygen intensity increasing both in operando and ex situ measurements.
36 MATERIALS SCIENCE↗
Practical guide to understanding goodness-of-fit metrics used in chemical state modeling of x-ray photoelectron spectroscopy data by synthetic line shapes using nylon as an example
Chemical state analysis of a sample surface through fitting bell-shaped curves to x-ray photoelectron spectroscopic polymer data is reviewed using nylon to introduce and discuss aspects of data analysis. Different strategies for modeling chemistry in nylon spectra are presented and in so doing, a case is made to include in published science the design logic and implementation in terms of line shapes and optimization parameter constraints between components in a peak model. Imperfections in line shape relative to the true shape for photoemission lines, when compensated for using constraints to optimization parameters, are shown to provide chemical state information about a sample that justify, for peak models constructed with these limitations, metrics for goodness-of-fit different from those expected for pulse-counted data.
Materials Science↗
Solid state chemical source for ammonia beam maser Patent
Solid state chemical source for ammonia beam masers
Robinson, M.↗
Revealing the Chemical State of Palladium in Operating In 2 O 3 Gas Sensors: Metallic Pd Enhances Sensing Response and Intermetallic In x Pd y Compound Blocks It
The sensing response of metal oxides activated with noble metal nanoparticles is significantly influenced by changes to the chemical state of corresponding elements under operating conditions. Here, a PdO/rh-In 2 O3 consisting of PdO nanoparticles loaded onto rhombohedral In 2 O 3 was studied as a gas sensor for H 2 gas (100–40000 ppm in an oxygen-free atmosphere) in the temperature range of 25–450 °C. The phase composition and chemical state of elements were examined by resistance measurements combined with synchrotron-based in situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy. As found, PdO/rh-In 2 O 3 undergoes a series of structural and chemical transformations during operation: from PdO to Pd/PdH x and finally to the intermetallic In x Pd y phase. The maximal sensing response (R N2 /R H2 ) of ~5 · 10 7 towards 40000 ppm (4 vol %) H 2 at 70 °C is correlated with the formation of PdH 0.706 /Pd. The In x Pd y intermetallic compounds formed around 250 °C significantly decrease the sensing response.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy
The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220–250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Chemical state mapping of simulant Chernobyl lava-like fuel containing material using micro-focused synchrotron X-ray spectroscopy
Uranium speciation and redox behaviour is of critical importance in the nuclear fuel cycle. X-ray absorption near-edge spectroscopy (XANES) is commonly used to probe the oxidation state and speciation of uranium, and other elements, at the macroscopic and microscopic scale, within nuclear materials. Two-dimensional (2D) speciation maps, derived from microfocus X-ray fluorescence and XANES data, provide essential information on the spatial variation and gradients of the oxidation state of redox active elements such as uranium. In the present work, we elaborate and evaluate approaches to the construction of 2D speciation maps, in an effort to maximize sensitivity to the U oxidation state at the U L 3 -edge, applied to a suite of synthetic Chernobyl lava specimens. Our analysis shows that calibration of speciation maps can be improved by determination of the normalized X-ray absorption at excitation energies selected to maximize oxidation state contrast. The maps are calibrated to the normalized absorption of U L 3 XANES spectra of relevant reference compounds, modelled using a combination of arctangent and pseudo-Voigt functions (to represent the photoelectric absorption and multiple-scattering contributions). We validate this approach by microfocus X-ray diffraction and XANES analysis of points of interest, which afford average U oxidation states in excellent agreement with those estimated from the chemical state maps. This simple and easy-to-implement approach is general and transferrable, and will assist in the future analysis of real lava-like fuel-containing materials to understand their environmental degradation, which is a source of radioactive dust production within the Chernobyl shelter.
36 MATERIALS SCIENCE↗
Effect of dielectric stoichiometry and interface chemical state on band alignment between tantalum oxide and platinum
The tantalum oxide–platinum interface electronic properties determined by X-ray photoelectron spectroscopy are found to depend on the dielectric stoichiometry and platinum chemical state. We demonstrate the slow charging of the tantalum oxide in cases of Ta{sub 2}O{sub 5}/Pt and Ta{sub 2}O{sub 5−y}/Pt interfaces under the X-ray irradiation. This behavior is proposed to be related to the charge accumulation at oxygen vacancies induced traps. Based on the proposed methodology, we define the intrinsic conductive band offset (CBO) ∼1.3 eV (both for Ta{sub 2}O{sub 5}/Pt and Ta{sub 2}O{sub 5−y}/Pt) and CBO after the full saturation of the traps charging ∼0.5 eV, while the last one defines the energy position of charged traps below the bottom of conduction band. We demonstrate also the pining at the both Ta{sub 2}O{sub 5}/Pt and Ta{sub 2}O{sub 5−y}/Pt interfaces even in the “intrinsic” state, apparently induced by the presence of additional interfacial states. No shifts of Ta4f line and band alignment in over stoichiometric Ta{sub 2}O{sub 5+x}/Pt structure during X-ray irradiation, as well as the absence of pinning, resulting in increase of CBO up to 2.3 eV are found. This behavior is related to the PtO{sub 2} interfacing layer formation at Ta{sub 2}O{sub 5+x}/Pt, blocking the charging of the surface states and associated dipole formation.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Investigation of the near-surface structures of polar InN films by chemical-state-discriminated hard X-ray photoelectron diffraction
Near-surface structures of polar InN films were investigated by laboratory-based hard X-ray photoelectron diffraction (HXPD) with chemical-state-discrimination. HXPD patterns from In 3d{sub 5/2} and N 1s core levels of the In-polar and N-polar InN films were different from each other and compared with the simulation results using a multiple-scattering cluster model. It was found that the near-surface structure of the In-polar InN film was close to the ideal wurtzite structure. On the other hand, on the N-polar InN film, defects-rich surface was formed. In addition, the existence of the In-polar domains was observed in the HXPD patterns.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Simultaneous enhancement of carrier mobility and concentration via tailoring of Al-chemical states in Al-ZnO thin films
Simultaneously achieving higher carriers concentration and mobility is a technical challenge against up-scaling the transparent-conductive performances of transparent-conductive oxides. Utilizing one order higher dense (∼1 × 10{sup 11} cm{sup −3}) plasmas (in comparison to the conventional direct current plasmas), highly c-axis oriented Al-doped ZnO films have been prepared with precise control over relative composition and chemical states of constituting elements. Tailoring of intrinsic (O vacancies) and extrinsic (ionic Al and zero-valent Al) dopants provide simultaneous enhancement in mobility and concentration of charge carriers. Room-temperature resistivity as low as 4.89 × 10{sup −4} Ω cm along the carrier concentration 5.6 × 10{sup 20} cm{sup −3} is obtained in 200 nm thick transparent films. Here, the control of atomic Al reduces the charge trapping at grain boundaries and subdues the effects of grain boundary scattering. A mechanism based on the correlation between electron-hole interaction and carrier mobility is proposed for degenerately doped wide band-gap semiconductors.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Interplay between chemical state, electric properties, and ferromagnetism in Fe-doped ZnO films
Valence state of Fe ions plays an important role in the physical properties of Fe doped ZnO films. Here, a series of Zn{sub 1-x}Fe{sub x}O films with different Fe concentrations (x = 0, 2.3, 5.4, 7.1, and 9.3 at. %) were prepared to investigate their structural, piezoelectric, ferroelectric, bipolar resistive switching properties, and electrical-control of ferromagnetism at room temperature. The structure characterizations indicate that the chemical state of Fe ions substituting Zn{sup 2+} site changes from Fe{sup 3+} to Fe{sup 2+} with the increase of Fe dopant concentration. We found enhanced piezoelectric and ferroelectric properties in Zn{sub 0.977}Fe{sub 0.023}O films with more Fe{sup 3+} due to the smaller Fe{sup 3+} ionic size in comparison with Zn{sup 2+} while the increase of Fe{sup 2+} concentration by a larger amount of Fe dopant results in the worse ferroelectric and piezoelectric performance. All Pt/Zn{sub 1-x}Fe{sub x}O/Pt devices show bipolar resistive switching properties. Especially, devices with lower Fe dopant concentration exhibit better endurance properties due to their higher crystalline quality. The variation of oxygen vacancies during resistive switching provides an opportunity to tune ferromagnetism of Fe-doped ZnO films, giving rise to the integration of charge and spin into a simple Pt/Zn{sub 1-x}Fe{sub x}O/Pt devices. The multifunctional properties of Fe-doped ZnO films are promising for communication systems and information storage devices.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Effect of the Chemical State of the Surface on the Relaxation of the Surface Shell Atoms in SiC and GaN Nanocrystals
The effect of the chemical state of the surface of nanoparticles on the relaxation in the near-surface layer was examined using the concept of the apparent lattice parameter (alp) determined for different diffraction vectors Q. The apparent lattice parameter is a lattice parameter determined either from an individual Bragg reflection, or from a selected region of the diffraction pattern. At low diffraction vectors the Bragg peak positions are affected mainly by the structure of the near-surface layer, while at high Q-values only the interior of the nano-grain contributes to the diffraction pattern. Following the measurements on raw (as prepared) powders we investigated powders cleaned by annealing at 400C under vacuum, and the same powders wetted with water. Theoretical alp-Q plots showed that the structure of the surface layer depends on the sample treatment. Semi-quantitative analysis based on the comparison of the experimental and theoretical alp-Q plots was performed. Theoretical alp-Q relations were obtained from the diffraction patterns calculated for models of nanocrystals with a strained surface layer using the Debye functions.
Palosz, B.↗
On the chemical state of Co oxide electrocatalysts during alkaline water splitting
Resonant inelastic X-ray scattering and high-resolution X-ray absorption spectroscopy were used to identify the chemical state of a Co electrocatalyst in situ during the oxygen evolution reaction. After anodic electrodeposition onto Au(111) from a Co 2+ -containing electrolyte, the chemical environment of Co can be identified to be almost identical to CoOOH. With increasing potentials, a subtle increase of the Co oxidation state is observed, indicating a non-stoichiometric composition of the working OER catalyst containing a small fraction of Co 4+ sites. In order to confirm this interpretation, we used density functional theory with a Hubbard- U correction approach to compute X-ray absorption spectra of model compounds, which agree well with the experimental spectra. Finally, in situ monitoring of catalyst local structure and bonding is essential in the development of structure-activity relationships that can guide the discovery of efficient and earth abundant water splitting catalysts.
Friebel, Daniel↗
Photoelectron Spectroscopy for Identification of Chemical States
The technique of X-ray photoelectron spectroscopy and the fundamental electronic interactions constituting the basis of the method will be discussed. The method provides information about chemical states ("oxidation states") of atoms in molecules. In addition, quantitative elemental analysis can be performed using the same method. On the basis of this information identification of chemical species is possible. Examples of applications are discussed with particular references to the study of smog particulate matter.
Novakov, T.↗