Enhancement of mineral density and mechanical properties in root caries treated with silver diammine fluoride and glass ionomer cement, with emphasis on silver ion distribution.

OBJECTIVES: This study aimed to measure the distribution of silver ion (Ag+), mineral recovery, and nanohardness in carious lesions and comprehensively evaluate the degree of dentin restoration. METHODS: Sixty human teeth with root caries were randomly assigned to the control, silver diammine fluoride (SDF) [Safo], and SDF+Glass ionomer cement (GIC) treatment [Safo+Fuji] groups. Micro-computed tomography (micro-CT) was performed at five time points for each sample before/after treatment to evaluate mineral density within and around carious lesions. Three months following treatment, 12 samples were selected for synchrotron radiation X-ray fluorescence analysis to evaluate Ag+ distribution, while 15 samples were selected for nanoindentation. Data were analyzed using Dunnett's T3 test for micro-CT and Wilcoxon rank sum test with Bonferroni correction (p = 0.017) for nanoindentation. The correlation between hardness and mineral change was analyzed using the Spearman rank correlation coefficient. RESULTS: The Safo and Safo+Fuji groups showed significantly higher mineral recovery rates than did the control group (p < 0.001). In the Safo group, Ag+ accumulated in the deeper layers rather than the superficial layer of caries. In the Safo+Fuji group, Ag+ was found evenly distributed throughout caries, with only a few Ag+ detected in the GIC layer. Hardness in the Safo+Fuji group was significantly higher compared with the Safo group at depths in the range of 10-50 µm. CONCLUSION: In the presence of GICs, SDF exhibited high remineralization capacity when diffusing throughout carious lesions over time. Combined treatment with SDF and GIC could strengthen root dentin even in the presence of caries. CLINICAL SIGNIFICANCE: We found that combination treatment with SDF and GIC could increase mineral density in caries and improve the hardness of the tooth structure compared with fluoride-based agents alone. These findings might pave the way for future clinical trials to determine the therapeutic potential of nanotechnology-based restorative materials.

Application of transition-edge sensors for micro-X-ray fluorescence measurements and micro-X-ray absorption near edge structure spectroscopy: a case study of uranium speciation in biotite obtained from a uranium mine.

In this study, we successfully applied a transition-edge sensor (TES) spectrometer as a detector for microbeam X-ray measurements from a synchrotron X-ray light source in the hard X-ray region to determine uranium (U) distribution at the micro-scale and its chemical species in biotite obtained from a U mine. It is difficult to separate the fluorescent X-ray of the U Lα1 line at 13.615 keV from that of the Rb Kα line at 13.395 keV in the X-ray fluorescence spectrum with an energy resolution of approximately 220 eV using a conventional silicon drift detector (SDD). Meanwhile, the fluorescent X-rays of U Lα1 and Rb Kα were fully separated by a TES with 50 eV energy resolution at an energy of around 13 keV. The successful peak separation by the TES led to an accurate mapping analysis of trace U in micro-X-ray fluorescence measurements and a decrease in the signal-to-background ratio in micro-X-ray absorption near edge structure spectroscopy. Thus, it could be a powerful tool for studying the U distribution and speciation in various environmental samples.

5D Analysis of Capacity Degradation in Battery Electrodes Enabled by Operando CT-XANES.

For devices encountering long-term stability challenges, a precise evaluation of degradation is of paramount importance. However, methods for comprehensively elucidating the degradation mechanisms in devices, particularly those undergoing dynamic chemical and mechanical changes during operation, such as batteries, are limited. Here, a method is presented using operando computed tomography combined with X-ray absorption near-edge structure spectroscopy (CT-XANES) that can directly track the evolution of the 3D distribution of the local capacity loss in battery electrodes during (dis)charge cycles, thereby enabling a five-dimensional (the 3D spatial coordinates, time, and chemical state) analysis of the degradation. This paper demonstrates that the method can quantify the spatiotemporal dynamics of the local capacity degradation within an electrode during cycling, which has been truncated by existing bulk techniques, and correlate it with the overall electrode performance degradation. Furthermore, the method demonstrates its capability to uncover the correlation among observed local capacity degradation within electrodes, reaction history during past (dis)charge cycles, and electrode microstructure. The method thus provides critical insights into the identification of degradation factors that are not available through existing methods, and therefore, will contribute to the development of batteries with long-term stability.

Oxidation and phase transfer of individual Cr-doped dendritic FeOx particles visualized by full-field nano-XAFS spectroimaging.

Iron oxides with various compositions and polymorphs have been widely used as compounds that require reversible redox properties, such as catalysts. However, partial decomposition during phase transitions often causes irreversible degradation of the redox properties of iron oxides. Cr doping into the crystalline framework of iron oxide dendrites improves the stability of the structural transformation of iron oxides. We spatially visualized the FeOx-dendrite phase distribution during oxidation in crystalline dendritic FeOx and Cr-FeOx particles by full-field nano-X-ray absorption fine structure spectroimaging. The spectroimaging visualized propagation in the phase transitions in the individual FeOx particles and changes in the phase transition behaviors of the Cr-FeOx particles. The statistical analysis of the spectroimaging data revealed the phase transition trends in parts of the FeOx and Cr-FeOx particles in three Fe density zones (particle thicknesses) and the probability densities of the phase proportions in the dendrites.

High-sensitive XANES analysis at Ce L2-edge for Ce in bauxites using transition-edge sensors: Implications for Ti-rich geological samples.

Accurate determination of cerium (Ce) valence state is important for interpreting the Ce anomaly in geological archives for (paleo)redox reconstruction. However, the routine application of Ce L3-edge X-ray absorption near-edge structure (XANES) spectroscopy for detecting trace Ce in geological samples can often be restricted by coexisting titanium (Ti) due to the proximity of their fluorescence emission lines. Therefore, the signal-to-noise ratio of Ce L3-edge XANES spectra may not be sufficiently high for high-quality spectroscopic analysis. This study introduces a semi-quantitative approach appropriate for Ti-rich, Ce-dilute geological materials by synchrotron-based X-ray measurement at the Ce L2-edge. First, the results confirm that Ce L2-edge XANES spectra are able to avoid overlapping Ti Kß emissions and provide more reliable information on the Ce valence state in Ti-rich materials relative to L3-edge XANES. Moreover, the application of transition-edge sensor (TES) could reach the higher sensitivity with better energy resolution than conventional silicon drift detector (SDD) to detect fluorescence X-ray (Ce Lß1). The investigation on bauxites developed from the Columbia River Basalts shows that combining Ce L2-edge XANES and TES allows for resolving weak Ce fluorescence lines at the L2-edge from Ti-rich, Ce-dilute samples (Ti/Ce mass ratio up to ∼6000, tens of ppm Ce). The outcome emphasizes the practical possibility of investigating Ce redox state in Ti-rich geological samples.

Experimental evidence of tetrahedral symmetry breaking in SiO2 glass under pressure.

Bimodal behavior in the translational order of silicon's second shell in SiO2 liquid at high temperatures and high pressures has been recognized in theoretical studies, and the fraction of the S state with high tetrahedrality is considered as structural origin of the anomalous properties. However, it has not been well identified in experiment. Here we show experimental evidence of a bimodal behavior in the translational order of silicon's second shell in SiO2 glass under pressure. SiO2 glass shows tetrahedral symmetry structure with separation between the first and second shells of silicon at low pressures, which corresponds to the S state structure reported in SiO2 liquid. On the other hand, at high pressures, the silicon's second shell collapses onto the first shell, and more silicon atoms locate in the first shell. These observations indicate breaking of local tetrahedral symmetry in SiO2 glass under pressure, as well as SiO2 liquid.

Broadband high-energy resolution hard x-ray spectroscopy using transition edge sensors at SPring-8.

We have succeeded in operating a transition-edge sensor (TES) spectrometer and evaluating its performance at the SPring-8 synchrotron x-ray light source. The TES spectrometer consists of a 240 pixel National Institute of Standards and Technology (NIST) TES system, and 220 pixels are operated simultaneously with an energy resolution of 4 eV at 6 keV at a rate of ∼1 c/s pixel-1. The tolerance for high count rates is evaluated in terms of energy resolution and live time fraction, leading to an empirical compromise of ∼2 × 103 c/s (all pixels) with an energy resolution of 5 eV at 6 keV. By utilizing the TES's wideband spectroscopic capability, simultaneous multi-element analysis is demonstrated for a standard sample. We conducted x-ray absorption near-edge structure (XANES) analysis in fluorescence mode using the TES spectrometer. The excellent energy resolution of the TES enabled us to detect weak fluorescence lines from dilute samples and trace elements that have previously been difficult to resolve due to the nearly overlapping emission lines of other dominant elements. The neighboring lines of As Kα and Pb Lα2 of the standard sample were clearly resolved, and the XANES of Pb Lα2 was obtained. Moreover, the x-ray spectrum from the small amount of Fe in aerosols was distinguished from the spectrum of a blank target, which helps us to understand the targets and the environment. These results are the first important step for the application of high resolution TES-based spectroscopy at hard x-ray synchrotron facilities.

Characterization of two types of cesium-bearing microparticles emitted from the Fukushima accident via multiple synchrotron radiation analyses.

A part of radiocesium emitted during the Fukushima nuclear accident was incorporated in glassy water-resistant microparticles, called Type-A particles, which are spherical with ~ 0.1 to 10 µm diameter and ~ 10-2 to 102 Bq cesium-137 (137Cs) radioactivity; they were emitted from Unit 2 or 3 of the Fukushima Daiichi Nuclear Power Plant. Meanwhile, Type-B particles, having various shapes, 50-400 µm diameter, and 101-104 Bq 137Cs radioactivity, were emitted from Unit 1. The chemical properties of these radioactive particles have been reported in detail, but previous studies investigated only a small number of particles, especially Type-B particles. We tried to understand radioactive particles systematically by analyzing a large number of particles. Micro-X-ray computed tomography combined with X-ray fluorescence analysis revealed the presence of many voids and iron-rich part within Type-B particles. The 137Cs concentration (Bq mm-3) of Type-A particles was ~ 10,000 times higher than that of Type-B particles. Among the Type-B particles, the spherical ones had higher concentration of volatile elements than the non-spherical ones. These differences suggested that Type-A particles were formed through gas condensation, whereas Type-B particles were formed through melt solidification. These findings might contribute to the safe decommissioning of reactors and environmental impact assessment.

Model building analysis - a novel method for statistical evaluation of Pt L3-edge EXAFS data to unravel the structure of Pt-alloy nanoparticles for the oxygen reduction reaction on highly oriented pyrolytic graphite.

Extended X-ray absorption fine structure (EXAFS) is a powerful tool to determine the local structure in Pt nanoparticles (NP) on carbon supports, active catalysts for fuel cells. Highly oriented pyrolytic graphite (HOPG) covered with Pt NP gives samples with flat surfaces that allow application of surface science techniques. However, the low concentration of Pt makes it difficult to obtain good quality EXAFS data. We have performed in situ highly sensitive BCLA-empowered Back Illuminated EXAFS (BCLA + BI-EXAFS) measurements on Pt alloy nanoparticles. We obtained high quality Pt L3-edge data. We have devised a novel analytical method (model building analysis) to determine the structure of multi-component nanoparticles from just a single absorption edge. The generation of large numbers of structural models and their comparison with EXAFS fits allows us to determine the structures of Pt-containing nanoparticles, catalysts for the oxygen reduction reaction. Our results show that PtCo, PtCoN and AuPtCoN form a Pt-shell during electrochemical dealloying and that the ORR activity is directly proportional to the Pt-Pt bond length.

3D Operando Imaging and Quantification of Inhomogeneous Electrochemical Reactions in Composite Battery Electrodes.

The performances of electrochemical systems such as solid-state batteries (SSBs) can be severely hindered by the three-dimensional (3D) and mesoscopically inhomogeneous electrochemical reactions that take place in the electrodes. However, the majority of existing methods for analyzing such inhomogeneous reactions are restricted to one- or two-dimensional observations. Herein, we performed 3D operando imaging of the mesoscopically inhomogeneous electrochemical reaction in a composite SSB electrode using hard X-ray computed-tomography with X-ray absorption near edge structure spectroscopy (CT-XANES). The 3D inhomogeneous reaction evolution during (dis)charge was successfully visualized for the first time. Furthermore, our 3D quantitative analysis unambiguously revealed the origin of the inhomogeneous reaction in the investigated electrode. Our results suggested that slow ion transport through active material particles can considerably restrict SSB performances. Our technique therefore provides new insights into the electrochemical reactions taking place in electrodes and enables us to maximize the performance of electrochemical systems.

Quantitative evaluation of the intratumoral distribution of platinum in oxaliplatin-treated rectal cancer: In situ visualization of platinum via synchrotron radiation X-ray fluorescence spectrometry.

Oxaliplatin (l-OHP), a platinum-based drug, is a key chemotherapeutic agent for colorectal cancer (CRC), but drug resistance and toxic effects have been major limitations of its use. Synchrotron radiation X-ray fluorescence spectrometry (SR-XRF) is a rapid, nondestructive technique for monitoring the distribution of metals and trace elements in cells or tissue samples. We applied SR-XRF to visualize the distribution of platinum and other elements in 30 rectal cancer specimens resected from patients who received l-OHP-based preoperative chemotherapy and quantified platinum concentration in the tumor epithelium and stroma, respectively, using calibration curves. The platinum concentration in rectal cancer tissue ranged 2.85-11.44 ppm, and the detection limit of platinum was 1.848 ppm. In the tumor epithelium, the platinum concentration was significantly higher in areas of degeneration caused by chemotherapy than in nondegenerated area (p < 0.001). Conversely, in the tumor stroma, the platinum concentration was significantly higher in patients with limited therapeutic responses than in those with strong therapeutic responses (p < 0.001). Furthermore, multivariate analysis illustrated that higher platinum concentration in the tumor stroma was an independent predictive factor of limited histologic response (odds ratio; 19.99, 95% confidence interval; 2.04-196.37, p = 0.013). This is the first study to visualize and quantify the distribution of platinum in human cancer tissues using SR-XRF. These results suggest that SR-XRF analysis may contribute to predicting the therapeutic effect of l-OHP-based chemotherapy by quantifying the distribution of platinum.

Visualization Analysis of Pt and Co Species in Degraded Pt3Co/C Electrocatalyst Layers of a Polymer Electrolyte Fuel Cell Using a Same-View Nano-XAFS/STEM-EDS Combination Technique.

In order to obtain a suitable design policy for the development of a next-generation polymer electrolyte fuel cell, we performed a visualization analysis of Pt and Co species following aging and degradation processes in membrane-electrode assembly (MEA), using a same-view. Nano-X-ray absorption fine structure (XAFS)/Scanning transmission electron microscope (STEM)-energy dispersive X-ray spectroscopy (EDS) technique that we developed to elucidate durability factors and degradation mechanisms of a MEA Pt3Co/C cathode electrocatalyst with higher activity and durability than a MEA Pt/C. In the MEA Pt3Co/C, after 5000 ADT-rec (rectangle accelerated durability test) cycles, unlike the MEA Pt/C, there was no oxidation of Pt. In contrast, Co oxidized and dissolved over a wide range of the cathode layer (∼70% of the initial Co amount). The larger the size of the cracks and pores in the MEA Pt/C and the smaller the ratio of Pt/ionomer of cracks and pores, the faster the rate of catalyst degradation. In contrast, there was no correlation between the size or Co/ionomer ratio of the cracks and pores and the Co dissolution of the MEA Pt3Co/C. It was shown that Co dissolved in the electrolyte region had an octahedral Co2+-O6 structure, based on a 150 nm × 150 nm nano-XAFS analysis. It was also shown that its existence suppressed the oxidation and dissolution of Pt. The MEA Pt3Co/C after 10,000 ADT-rec cycles had many cracks and pores in the cathode electrocatalyst layer, and about 90% of Co had been dissolved and removed from the cathode layer. We discovered a metallic Pt-Co alloy band in the electrolyte region of 300-400 nm from the cathode edge and square planar Pt2+-O4 species and octahedral Co2+-O6 species in the area between the cathode edge and the Pt-Co band. The transition of Pt and Co chemical species in the Pt3Co/C cathode electrocatalyst in the MEA during the degradation process, as well as a fuel cell deterioration suppression process by Co were visualized for the first time at the nano scale using the same-view nano-XAFS/STEM-EDS combination technique that can measure the MEA under a humid N2 atmosphere while maintaining the working environment for a fuel cell.

SPring-8 BL36XU: Synchrotron Radiation X-Ray-Based Multi-Analytical Beamline for Polymer Electrolyte Fuel Cells under Operating Conditions.

We designed and constructed a beamline BL36XU at the 8 GeV synchrotron radiation facility SPring-8 to provide information required for the development of next-generation polymer electrolyte fuel cells (PEFCs) by clarifying the dynamic aspects of structures and electronic states of cathode catalysts under PEFC operating conditions and in the deterioration processes by accelerated durability test protcols. To investigate the mechanism and degradation process for the cathode electrocatalysis in practical PEFCs, we developed advanced time- and spatially-resolved in-situ/operando X-ray absorption fine structure measurement systems and complementary analytical systems (X-ray emission spectroscopy (XES), X-ray diffraction (XRD), X-ray computer tomography (CT) and hard X-ray photoelectron spectroscopy (HAXPES)) and combined them to develop multi-analytical systems at BL36XU. Multi-analytical systems are very powerful for observing spatial-temporal features of the transient processes occurring in complex systems such as PEFCs. This account describes the design, performance, and research results of the BL36XU and multi-analytical in-situ/operando systems.

Development of Surface Fluorescence X-Ray Absorption Fine Structure Spectroscopy Using a Laue-Type Monochromator.

Surface fluorescence X-ray absorption fine structure (XAFS) spectroscopy using a Laue-type monochromator has been developed to acquire structural information about metals with a very low concentrate on a flat highly oriented pyrolytic graphite (HOPG) surface in the presence of electrolytes. Generally, surface fluorescence XAFS spectroscopy is hindered by strong scattering from the bulk, which often chokes the pulse counting detector. In this work, we show that a bent crystal Laue analyzer (BCLA) can efficiently remove the scattered X-rays from the bulk even in the presence of solution. We applied the technique to submonolayer (∼1014  atoms cm-2 ) Pt on HOPG and successfully obtained high signal/noise in situ XAFS data in combination with back-illuminated fluorescence XAFS (BI-FXAFS) spectroscopy. This technique allows in situ XAFS measurements of flat electrode surfaces to be performed in the presence of electrolytes.

Operando XAFS Imaging of Distribution of Pt Cathode Catalysts in PEFC MEA.

Three-dimensional imaging using X-ray as a probe is state-of-the-art for the characterization of heterogeneous materials. In addition to simple imaging of sample morphology, imaging of elemental distribution and chemical states provides advanced maps of key structural parameters of functional materials. The combination of X-ray absorption fine structure (XAFS) spectroscopy and three-dimensional imaging such as computed tomography (CT) can visualize the three-dimensional distribution of target elements, their valence states, and local structures in a non-destructive manner. In this personal account, our recent results on the three-dimensional XAFS imaging for Pt cathode catalysts in the membrane electrode assembly (MEA) of polymer electrolyte fuel cell (PEFC) are introduced. The distribution and chemical states of Pt cathode catalysts in MEAs remarkably change under PEFC operating conditions, and the 3D XAFS imaging revealed essential events in PEFC MEAs.

Observation of Degradation of Pt and Carbon Support in Polymer Electrolyte Fuel Cell Using Combined Nano-X-ray Absorption Fine Structure and Transmission Electron Microscopy Techniques.

It is hard to directly visualize spectroscopic and atomic-nanoscopic information on the degraded Pt/C cathode layer inside polymer electrolyte fuel cell (PEFC). However, it is mandatory to understand the preferential area, sequence, and relationship of the degradations of Pt nanoparticles and carbon support in the Pt/C cathode layer by directly observing the Pt/C cathode catalyst for the development of next-generation PEFC cathode catalysts. Here, the spectroscopic, chemical, and morphological visualization of the degradation of Pt/C cathode electrocatalysts in PEFC was performed successfully by a same-view combination technique of nano-X-ray absorption fine structure (XAFS) and transmission electron microscopy (TEM)/scanning TEM-energy-dispersive spectrometry (EDS) under a humid N2 atmosphere. The same-view nano-XAFS and TEM/STEM-EDS imaging of the Pt/C cathode of PEFC after triangular-wave 1.0-1.5 VRHE (startup/shutdown) accelerated durability test (tri-ADT) cycles elucidated the site-selective area, sequence, and relationship of the degradations of Pt nanoparticles and carbon support in the Pt/C cathode layer. The 10 tri-ADT cycles caused a carbon corrosion to reduce the carbon size preferentially in the boundary regions of the cathode layer with both electrolyte and holes/cracks, accompanied with detachment of Pt nanoparticles from the degraded carbon. After the decrease in the carbon size to less than 8 nm by the 20 tri-ADT cycles, Pt nanoparticles around the extremely corroded carbon areas were found to transform and dissolve into oxidized Pt2+-O4 species.

Non-contact electric potential measurements of electrode components in an operating polymer electrolyte fuel cell by near ambient pressure XPS.

Photoelectron spectroscopy has the advantage of providing electric potentials by non-contact measurements based on the kinetic energy shift in component potential. We performed operando hard X-ray photoelectron spectroscopy (HAXPES) measurements with an 8 keV excitation source to measure the shift in electron kinetic energies as a function of the voltages of all the components at the anode and cathode electrodes of a polymer electrolyte fuel cell (PEFC). At the cathode electrode, when we increase the voltage between the cathode and anode from 0.2 to 1.2 V, the O 1s and F 1s peaks shift to a lower binding energy and the magnitude of the energy shift is equal to the voltage. The Pt 3d and C 1s peaks do not shift with the voltage since platinum nanoparticles and carbon supports at the cathode electrode have ground contact. In contrast to the cathode electrode, the peak shifts of all the components at the anode electrode show the same amount of shift as the voltages. It is clear that the change in the potential difference occurs only in an electrical double layer at the interface between the cathode electrode (Pt/C) and the electrolyte (Nafion and water), and that the anode electrode is in equilibrium as a pseudo-hydrogen electrode. Moreover, the electric potential variation of the cathode electrode in a PEFC under a power generation condition was also directly detected by operando HAXPES.

Operando 3D Visualization of Migration and Degradation of a Platinum Cathode Catalyst in a Polymer Electrolyte Fuel Cell.

The three-dimensional (3D) distribution and oxidation state of a Pt cathode catalyst in a practical membrane electrode assembly (MEA) were visualized in a practical polymer electrolyte fuel cell (PEFC) under fuel-cell operating conditions. Operando 3D computed-tomography imaging with X-ray absorption near edge structure (XANES) spectroscopy (CT-XANES) clearly revealed the heterogeneous migration and degradation of Pt cathode catalyst in an MEA during accelerated degradation test (ADT) of PEFC. The degradative Pt migration proceeded over the entire cathode catalyst layer and spread to MEA depth direction into the Nafion membrane.

In situ study of oxidation states of platinum nanoparticles on a polymer electrolyte fuel cell electrode by near ambient pressure hard X-ray photoelectron spectroscopy.

We performed in situ hard X-ray photoelectron spectroscopy (HAXPES) measurements of the electronic states of platinum nanoparticles on the cathode electrocatalyst of a polymer electrolyte fuel cell (PEFC) using a near ambient pressure (NAP) HAXPES instrument having an 8 keV excitation source. We successfully observed in situ NAP-HAXPES spectra of the Pt/C cathode catalysts of PEFCs under working conditions involving water, not only for the Pt 3d states with large photoionization cross-sections in the hard X-ray regime but also for the Pt 4f states and the valence band with small photoionization cross-sections. Thus, this setup allowed in situ observation of a variety of hard PEFC systems under operating conditions. The Pt 4f spectra of the Pt/C electrocatalysts in PEFCs clearly showed peaks originating from oxidized Pt(ii) at 1.4 V, which unambiguously shows that Pt(iv) species do not exist on the Pt nanoparticles even at such large positive voltages. The water oxidation reaction might take place at that potential (the standard potential of 1.23 V versus a standard hydrogen electrode) but such a reaction should not lead to a buildup of detectable Pt(iv) species. The voltage-dependent NAP-HAXPES Pt 3d spectra revealed different behaviors with increasing voltage (0.6 → 1.0 V) compared with decreasing voltage (1.0 → 0.6 V), showing a clear hysteresis. Moreover, quantitative peak-fitting analysis showed that the fraction of non-metallic Pt species matched the ratio of the surface to total Pt atoms in the nanoparticles, which suggests that Pt oxidation only takes place at the surface of the Pt nanoparticles on the PEFC cathode, and the inner Pt atoms do not participate in the reaction. In the valence band spectra, the density of electronic states near the Fermi edge reduces with decreasing particle size, indicating an increase in the electrocatalytic activity. Additionally, a change in the valence band structure due to the oxidation of platinum atoms was also observed at large positive voltages. The developed apparatus is a valuable in situ tool for the investigation of the electronic states of PEFC electrocatalysts under working conditions.

Imaging of Oxygen Diffusion in Individual Platinum/Ce2 Zr2 Ox Catalyst Particles During Oxygen Storage and Release.

The spatial distribution of Ce(3+) and Ce(4+) in each particle of Ce2 Zr2 Ox in a three-way conversion catalyst system was successfully imaged during an oxygen storage/release cycle by scanning X-ray absorption fine structure (XAFS) using hard X-ray nanobeams. For the first time, nano-XAFS imaging visualized and identified the modes of non-uniform oxygen diffusion from the interface of Pt catalyst and Ce2 Zr2 Ox support and the active parts in individual catalyst particles.