RESUMEN
Many unique adsorption properties of metal-organic frameworks (MOFs) have been revealed by diffraction crystallography, visualizing their vacant and guest-loaded crystal structures at the molecular scale. However, it has been challenging to see the spatial distribution of the adsorption behaviors throughout a single MOF particle in a transient equilibrium state. Here, we report three-dimensional (3D) visualization of molecular adsorption behaviors in a single crystalline particle of a MOF by in situ X-ray absorption fine structure spectroscopy combined with computed tomography for the first time. The 3D maps of water-coordinated Co sites in a 100 µm-scale MOF-74-Co crystal were obtained with 1 µm spatial resolution under several water vapor pressures. Through the visualization of the water vapor adsorption process, 3D spectroimaging revealed the mechanism and spatial heterogeneity of guest adsorption inside a single particle of a crystalline MOF.
RESUMEN
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.
RESUMEN
In situ 3D computed tomography imaging with statistical analysis successfully revealed the water accumulation and drainage characteristics in the stacked gas diffusion layers (GDLs) and membrane electrode assembly (MEA) of a polymer electrolyte fuel cell. Efficient water drainage at the interface between the cathode GDL and MEA was confirmed upon supplying oxygen to the cathode.
RESUMEN
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.
RESUMEN
We have investigated the S adsorption behaviours on Pt (average particle diameter of â¼2.6 nm) and Pt3Co (â¼3.0 nm) anode and cathode electrode catalysts in polymer electrolyte fuel cells (PEFCs) under working conditions for the fresh state just after the aging process and also the degraded state after accelerated degradation tests (ADT), by studying near ambient pressure hard X-ray photoelectron spectroscopy (HAXPES). S 1s HAXPES of both the anode and cathode electrodes shows not only the principal S species from the sulfonic acid group (-SO3H) in the Nafion electrolyte but also other characteristic S species such as zero-valent S (S0) adsorbed on the carbon support and anionic S (S2-) adsorbed on the Pt electrode. The S2- species on Pt should be ascribed to S contamination poisoning the Pt catalyst electrode. The S2- species on the cathode can be oxidatively removed by applying a high cathode-anode bias voltage (≥0.8 V) to form SO32-, while at the anode the S2- species cannot be eliminated because of reductive environment in hydrogen gas. The important finding is the difference in S adsorption behaviours between the Pt/C and Pt3Co/C electrodes after ADT. After ADT, the Pt/C anode electrode exhibits much larger S2- adsorption than the Pt3Co/C anode electrode. This indicates that the Pt3Co/C anode is more desirable than the Pt/C one from the viewpoint of S poisoning. The reason for more tolerance of the Pt3Co/C anode catalyst against S poisoning after ADT can be ascribed to the more negative charge of the surface Pt atoms in the Pt3Co/C catalyst than those in the Pt/C one, thus yielding a weaker interaction between the surface Pt and the anionic S species as S2-, SO32-, and SO42-. A similar behaviour was observed also in the cathode catalyst. The present findings will nevertheless provide important information to design novel Pt-based PEFC electrodes with higher performance and longer durability.
RESUMEN
The surface freezing transition of a mixed adsorbed film containing cetyltrimethylammonium chloride (CTAC) and n-hexadecanol (C16OH) was utilized at the dodecane-water interface to control the stability of oil-in-water (O/W) emulsions. The corresponding surface frozen and surface liquid mixed adsorbed films were characterized using interfacial tensiometry and X-ray reflectometry. The emulsion samples prepared in the temperature range of the surface frozen and surface liquid phases showed a clear difference in their stability: the emulsion volume decreased continuously right after the emulsification in the surface liquid region, while it remained constant or decreased at a much slower rate in the surface frozen region. Compared to the previously examined CTAC-tetradecane mixed adsorbed film, the surface freezing temperature increased from 9.5 to 25.0 °C due to the better chain matching between CTAC and C16OH and higher surface activity of C16OH. This then renders such systems much more attractive for practical applications.
RESUMEN
The synchronizing measurements of both cyclic voltammograms (CVs) and real-time quick XAFSs (QXAFSs) for Pt/C cathode electrocatalysts in a membrane electrode assembly (MEA) of polymer electrolyte fuel cells (PEFCs) treated by anode-gas exchange (AGEX) and cathode-gas exchange (CGEX) cycles (startup/shutdown conditions of FC vehicles) were performed for the first time to understand the opposite effects of the AGEX and CGEX treatments on the Pt/C performance and durability and also the contradiction between the electrochemical active surface area (ECSA) decrease and the performance increase by CGEX treatment. While the AGEX treatment decreased both the ECSA and performance of MEA Pt/C due to carbon corrosion, it was found that the CGEX treatment decreased the ECSA but increased the Pt/C performance significantly due to high-index (331) facet formation (high-resolution STEM) and hence the suppression of strongly bound Pt-oxide formation at cathode Pt nanoparticle surfaces. Transient QXAFS time-profile analysis for the MEA Pt/C also revealed a direct relationship between the electrochemical performance or durability and transient kinetics of the Pt/C cathode.
RESUMEN
We developed a multi-analysis system that can measure in situ time-resolved quick XAFS (QXAFS) and in situ three-dimensional XAFS-CT spatial imaging in the same area of a cathode electrocatalyst layer in a membrane-electrode assembly (MEA) of a polymer electrolyte fuel cell (PEFC) at the BL36XU beamline of SPring-8. The multi-analysis system also achieves ex situ two-dimensional nano-XAFS/STEM-EDS same-view measurements of a sliced MEA fabricated from a given place in the XAFS-CT imaged area at high spatial resolutions under a water-vapor saturated N2 atmosphere using a same-view SiN membrane cell. In this study, we applied the combination method of time-resolved QXAFS/3D XAFS-CT/2D nano-XAFS/STEM-EDS for the first time for the visualization analysis of the anode-gas exchange (AGEX) (simulation of the start-up/shut-down of PEFC vehicles) degradation process of a PEFC MEA Pt/C cathode. The AGEX cycles bring about serious irreversible degradation of both Pt nanoparticles and carbon support due to a spike-like large voltage increase. We could visualize the three-dimensional distribution and two-dimensional depth map of the amount, oxidation state (valence), Pt2+ elution, detachment, and aggregation of Pt species and the formation of carbon voids, where the change and movement of the Pt species in the cathode catalyst layer during the AGEX cycles did not proceed exceeding the 1 µm region. It is very different from the case of an ADT (an accelerated durability test between 0.6-1.0 VRHE)-degraded MEA. We discuss the spatiotemporal behavior of the AGEX degradation process and the degradation mechanism.
RESUMEN
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.
RESUMEN
Cr-Loaded iron oxide with a dendritic crystalline structure was synthesized and the reversible crystalline phase transition during redox cycling of the iron oxide was investigated. X-ray diffraction and transmission electron microscopy analyses revealed that Cr was well dispersed and loaded in the iron oxide dendrite crystals, whose lattice constant was dependent on the Cr loading. Temperature-programmed oxidation and reduction experiments revealed the reversible redox properties of the Cr-loaded iron oxide dendrites, whose redox temperature was found to be lower than that of Cr-free iron oxide dendrites. In situ Fe K-edge and Cr K-edge X-ray absorption near-edge structure (XANES) analysis indicated that Cr loading extended the redox reaction window for conversion between Fe3O4 and γ-Fe2O3 owing to compressive lattice strain in the iron oxide spinel structures.