Structure of Atomically Dispersed Pt in a SnO2 Thin Film under Reaction Conditions: Origin of Its High Performance in Micro Electromechanical System Gas Sensor Catalysis.

A battery-driven micro electromechanical system (MEMS) gas sensor has been developed for household safety when using natural gas. The heart of the MEMS gas sensor is a 7.5 at % Pt-SnO2 thin film catalyst deposited on the SnO2 sensor layer. The catalyst enhances the sensitivity to methane, though its structure under working conditions is unclear. In this study, in situ XAFS was applied to a 7.5 at % Pt-SnO2 catalyst layer deposited on a Si substrate, and we demonstrated that atomically dispersed Pt maintains its lattice position in SnO2 with a small loss of surrounding lattice oxygen in the presence of 1% CH4 and a more reducing gas of 1% H2 at the reaction temperature (703 K), i.e., no Pt aggregation is observed. The lost oxygen is easily recovered by re-oxidation by air. This work has revealed that the atomically dispersed Pt in the SnO2 lattice is the active structure and it is stable even under reaction conditions, which guarantees a long lifetime for the gas sensor.

Aggregation tendency of guest Fe in NaCo1-xFexO2 (x < 0.1) as investigated by systematic EXAFS analysis.

In transition metal (M) compounds, the partial substitution of the host transition metal (Mh) to guest one (Mg) is effective to improve the functionality. To microscopically comprehend the substitution effect, degree of distribution of Mg is crucial. Here, we propose that a systematic EXAFS analysis against the Mg concentration can reveal the spatial distribution of Mg. We chose NaCo1-xFexO2 as a prototypical M compound and investigated the local intermetal distance around the guest Fe [dFe-M(x)] against Fe concentration (x). dFe-M(x) steeply increased with x, reflecting the larger ionic radius of high-spin Fe3+. The x-dependence of dFe-M(x) was analyzed by an empirical equation, [Formula: see text], where dFe-Fe and dFe-Co are the Fe-Fe and Co-Fe distances, respectively. The parameter s represents degree of distribution of Fe; s = 1, > 1, < 1 are for random, attractive, and repulsive distribution, respectively. The obtained s value (= 4.8) indicates aggregation tendency of guest Fe.

Invariant nature of substituted element in metal-hexacyanoferrate.

The chemical substitution of a transition metal (M) is an effective method to improve the functionality of materials. In order to design the highly functional materials, we first have to know the local structure and electronic state around the substituted element. Here, we systematically investigated the local structure and electronic state of the host (M h) and guest (M g) transition metals in metal-hexacyanoferrate (M-HCF), Na x (M h, M g)[Fe(CN)6] y (1.40 < x < 1.60 and 0.85 < y < 0.90), by means of extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) analyses. The EXAFS and XANES analyses revealed that the local structure and electronic state around M g are essentially the same as those in the pure compound, i.e, M g-HCF. Such an invariant nature of M g in M-HCF is in sharp contrast with that in layered oxide, in which the M g valence changes so that local M g-O distance (d M-Og) approaches the M h-O distance (d M-Oh).

Multiple-wavelength neutron holography with pulsed neutrons.

Local structures around impurities in solids provide important information for understanding the mechanisms of material functions, because most of them are controlled by dopants. For this purpose, the x-ray absorption fine structure method, which provides radial distribution functions around specific elements, is most widely used. However, a similar method using neutron techniques has not yet been developed. If one can establish a method of local structural analysis with neutrons, then a new frontier of materials science can be explored owing to the specific nature of neutron scattering-that is, its high sensitivity to light elements and magnetic moments. Multiple-wavelength neutron holography using the time-of-flight technique with pulsed neutrons has great potential to realize this. We demonstrated multiple-wavelength neutron holography using a Eu-doped CaF2 single crystal and obtained a clear three-dimensional atomic image around trivalent Eu substituted for divalent Ca, revealing an interesting feature of the local structure that allows it to maintain charge neutrality. The new holography technique is expected to provide new information on local structures using the neutron technique.

Tellurium Distribution and Speciation in Contaminated Soils from Abandoned Mine Tailings: Comparison with Selenium.

The distribution and chemical species of tellurium (Te) in contaminated soil were determined by a combination of microfocused X-ray fluorescence (µ-XRF), X-ray diffraction (µ-XRD), and X-ray absorption fine structure (µ-XAFS) techniques. Results showed that Te was present as a mixture of Te(VI) and Te(IV) species, while selenium (Se) was predominantly present in the form of Se(IV) in the soil contaminated by abandoned mine tailings. In the contaminated soil, Fe(III) hydroxides were the host phases for Se(IV), Te(IV), and Te(VI), but Te(IV) could be also retained by illite. The difference in speciation and solubility of Se and Te in soil can result from different structures of surface complexes for Se and Te onto Fe(III) hydroxides. Furthermore, our results suggest that the retention of Te(IV) in soil could be relatively weaker than that of Te(VI) due to structural incorporation of Te(VI) into Fe(III) hydroxides. These findings are of geochemical and environmental significance for better understanding the solubility, mobility, and bioavailability of Te in the surface environment. To the best of our knowledge, this is the first study reporting the speciation and host phases of Te in field soil by the µ-XRF-XRD-XAFS techniques.

Local structures around the substituted elements in mixed layered oxides.

The chemical substitution of a transition metal (M) is an effective method to improve the functionality of a material, such as its electrochemical, magnetic, and dielectric properties. The substitution, however, causes local lattice distortion because the difference in the ionic radius (r) modifies the local interatomic distances. Here, we systematically investigated the local structures in the pure (x = 0.0) and mixed (x = 0.05 or 0.1) layered oxides, Na(M1-xM'x)O2 (M and M' are the majority and minority transition metals, respectively), by means of extended X-ray absorption fine structure (EXAFS) analysis. We found that the local interatomic distance (dM-O) around the minority element approaches that around the majority element to reduces the local lattice distortion. We further found that the valence of the minority Mn changes so that its ionic radius approaches that of the majority M.

Degradation mechanism of a high-performance real micro gas sensor, as determined by spatially resolved XAFS.

Of late, battery-driven high-performance gas sensors have gained acceptability in practical usage, whose atomic-scale structure has been revealed by µ-fluorescence X-ray absorption fine structure analysis. We studied the chemical distribution of Pd species in the Pd/Al2O3 catalyst overlayer in the real gas sensor at various degrees of deterioration. In a freshly prepared sensor, all Pd species were in the PdO form; in a heavily deteriorated sensor, Pd/Al2O3 in the external region changed to metallic Pd particles, while the PdO structure in the inner region near the heater remained unchanged. The Pd species distribution was in agreement with the simulated thermal distribution. Temperature control was crucial to maintain the high performance of the gas sensor. The improved sensor allows homogeneous heating and has a lifetime of more than 5 years.

A high-temperature in situ cell with a large solid angle for fluorescence X-ray absorption fine structure measurement.

We present the design and performance of a high-temperature in situ cell with a large solid angle for fluorescence X-ray absorption fine structure (XAFS) spectra. The cell has a large fluorescence XAFS window (116 mm(ϕ)) near the sample in the cell, realizing a large half-cone angle of 56°. We use a small heater (25 × 35 mm(2)) to heat the sample locally to 873 K. We measured a Pt-SnO2 thin layer on a Si substrate at reaction conditions having a high activity. In situ measurement enables the analysis of the difference XAFS spectra between before and during the reaction to reveal the structure change during the operation.

Improvement of a Real Gas-Sensor for the Origin of Methane Selectivity Degradation by µ-XAFS Investigation.

We have directly investigated the chemical state of the Pd species in a real µ-gas sensor device by examining the µ-fluorescence X-ray absorption fine structure. The µ-gas sensor device was heavily damaged by a heating process in which the temperature was ill-controlled, resulting in decrease of methane selectivity. We found that the PdO in the fresh µ-gas sensor was reduced to Pd metal particles as the methane selectivity decreased. Based on the investigation results, we modified the device structure so as to heat up homogeneously. The lifetime of the sensor was then successfully increased by more than 5 years.

X-ray-induced reduction of Au ions in an aqueous solution in the presence of support materials and in situ time-resolved XANES measurements.

Synchrotron X-ray-induced reduction of Au ions in an aqueous solution with or without support materials is reported. To clarify the process of radiation-induced reduction of metal ions in aqueous solutions in the presence of carbon particles as support materials, in situ time-resolved XANES measurements of Au ions were performed under synchrotron X-ray irradiation. XANES spectra were obtained only when hydrophobic carbon particles were added to the precursor solution containing Au ions. Changes in the shape of the XANES spectra indicated a rapid reduction from ionic to metallic Au in the precursor solution owing to synchrotron X-ray irradiation. In addition, the effects of the wettability of the carbon particles on the deposited Au metallic spots were examined. The deposited Au metallic spots were different depending on the relationship of surface charges between metal precursors and support materials. Moreover, a Au film was obtained as a by-product only when hydrophilic carbon particles were added to the precursor solution containing the Au ions.

In situ back-side illumination fluorescence XAFS (BI-FXAFS) studies on platinum nanoparticles deposited on a HOPG surface as a model fuel cell: a new approach to the Pt-HOPG electrode/electrolyte interface.

We measured the in situ polarization-dependent X-ray absorption fine structure of platinum nanoparticles (PtNPs) deposited on a flat highly oriented pyrolytic graphite (HOPG) substrate under electrochemical conditions using a back-side illumination method. In this method, the thin HOPG substrate with PtNPs deposited on one side was used as a window for incident and fluorescent X-rays, as well as an electrode. A bent crystal Laue analyzer (BCLA) was applied to the extraction of the Pt Lα fluorescent X-ray signals from strong scattered X-rays. Pt L3 edge XAFS spectra were observed for various electrode potentials and polarization directions.

In situ observation of carrier transfer in the Mn-oxide/Nb:SrTiO3 photoelectrode by X-ray absorption spectroscopy.

The Mn-oxide/Nb:SrTiO3 photoelectrode for oxygen evolution reaction was investigated by in situ Mn K-edge XAFS spectroscopy under UV irradiation. The oxidization of the Mn oxide was observed via photoexcited carrier transfer, which results in the positive potential shift of the Mn oxide cocatalyst toward oxygen evolution reaction.

Structural analysis of sonochemically prepared Au/Pd nanoparticles dispersed in porous silica matrix.

Bimetallic Au/Pd nanoparticles supported on a silica matrix were prepared by an ultrasonic technique. The samples heat-treated at 100, 200, 300 and 400 degrees C were examined with techniques of XRD (X-ray diffraction), TEM and XAS (X-ray absorption spectrometry) for studying correlation between their structure and the catalytic activity of hydrogenation of cyclohexene. Even after the heat treatment at 400 degrees C, the particles were smaller than 20 nm and well dispersed in the matrix without agglomeration nor sintering. Results of the XRD, TEM and XAS indicated that the as-prepared particles have a core/shell structure of Au/Pd and transform into a random alloy at 300 degrees C. The catalysis seemed to be deactivated by alloying.