Ceria-Doped Ni/SBA-16 Catalysts for Dry Reforming of Methane

Ni-ceria nanoparticles (Ni/Ce = 1/1) in the cage-like pores of SBA-16 were prepared and evaluated in methane dry reforming reactions. Coexistence of ceria in NiCe/SBA-16 resulted in forming uniformly sized Ni particles (av. 5.7 nm) within the mesopores of SBA-16, because of the confinement effect from the framework of SBA-16 and the strong interaction between Ni and ceria. Ceria addition facilitated the reduction of NiCe/SBA-16 compared with Ni/SBA-16, and Ce³⁺ was the dominant species in both fresh and used NiCe/SBA-16 catalysts, as determined by Ce L_III-edge X-ray absorption near-edge structure (XANES). The methane conversion was much more stable on NiCe/SBA-16 than on Ni/CeO₂ and Ni/SBA-16 in the methane dry reforming at 973 K during a 100 h reaction period; the deactivation of the Ni catalyst and the collapse of the SBA-16 framework were preferably suppressed for NiCe/SBA-16 under the reaction conditions. The remarkable effect of ceria on the structural stability of both the active Ni particles and the SBA-16 framework led to the consistent catalytic performance of NiCe/SBA-16 in methane dry reforming

Supplementary document for X-ray ptychographic and fluorescence microscopy using virtual single-pixel imaging-based deconvolution with accurate probe images - 6521745.pdf

Preparation process for obtaining blur kernels, reconstruction results of Ta test chart without considering probe variation, and deconvolution results of STXM images of ZnS particles

Size Regulation and Stability Enhancement of Pt Nanoparticle Catalyst via Polypyrrole Functionalization of Carbon-Nanotube-Supported Pt Tetranuclear Complex

A novel multiwall carbon nanotube (MWCNT) and polypyrrole (PPy) composite was found to be useful for preparing durable Pt nanoparticle catalysts of highly regulated sizes. A new pyrene-functionalized Pt₄ complex was attached to the MWCNT surface which was functionalized with PPy matrix to yield Pt₄ complex/PPy/MWCNT composites without decomposition of the Pt₄ complex units. The attached Pt₄ complexes in the composite were transformed into Pt⁰ nanoparticles with sizes of 1.0–1.3 nm at a Pt loading range of 2 to 4 wt %. The Pt nanoparticles in the composites were found to be active and durable catalysts for the <i>N</i>-alkylation of aniline with benzyl alcohol. In particular, the Pt nanoparticles with PPy matrix exhibited high catalyst durability in up to four repetitions of the catalyst recycling experiment compared with nonsize-regulated Pt nanoparticles prepared without PPy matrix. These results demonstrate that the PPy matrix act to regulate the size of Pt nanoparticles, and the PPy matrix also offers stability for repeated usage for Pt nanoparticle catalysis

Rate Enhancements in Structural Transformations of Pt–Co and Pt–Ni Bimetallic Cathode Catalysts in Polymer Electrolyte Fuel Cells Studied by in Situ Time-Resolved X‑ray Absorption Fine Structure

In situ time-resolved X-ray absorption fine structure spectra of Pt/C, Pt₃Co/C, and Pt₃Ni/C cathode electrocatalysts in membrane electrode assemblies (catalyst loading: 0.5 mg_metal cm^–2) were successfully measured every 100 ms for a voltage cycling process between 0.4 and 1.0 V. Systematic analysis of in situ time-resolved X-ray absorption near-edge structure and extended X-ray absorption fine structure spectra in the molecular scale revealed the structural kinetics of the Pt and Pt₃M (M = Co, Ni) bimetallic cathode catalysts under polymer electrolyte fuel cell operating conditions, and the rate constants of Pt charging, Pt–O bond formation/breaking, and Pt–Pt bond breaking/re-formation relevant to the fuel cell performances were successfully determined. The addition of the 3d transition metals to Pt reduced the Pt oxidation state and significantly enhanced the reaction rates of Pt discharging, Pt–O bond breaking, and Pt–Pt bond re-forming in the reductive process from 1.0 to 0.4 V

Kinetics and Mechanism of Redox Processes of Pt/C and Pt₃Co/C Cathode Electrocatalysts in a Polymer Electrolyte Fuel Cell during an Accelerated Durability Test

The degradation of Pt electrocatalysts in membrane electrode assemblies (MEAs) of polymer electrolyte fuel cells under working conditions is a serious problem for their practical use. Here we report the kinetics and mechanism of redox reactions at the surfaces of Pt/C and Pt₃Co/C cathode electrocatalysts during catalyst degradation processes by an accelerated durability test (ADT) studied by operando time-resolved X-ray absorption fine structure (XAFS) spectroscopy. Systematic analysis of a series of Pt L_III-edge time-resolved XAFS spectra measured every 100 ms at different degradation stages revealed changes in the kinetics of Pt redox reactions on Pt/C and Pt₃Co/C cathode electrocatalysts. In the case of Pt/C, as the number of ADT cycles increased, structural changes for Pt redox reactions (charging, surface, and subsurface oxidation) became less sensitive because of the agglomeration of catalyst particles. It was found that their rate constants were almost constant independent of the agglomeration of the Pt electrocatalyst. On the other hand, in the case of Pt₃Co/C, the rate constants of the redox reactions of the cathode electrocatalyst gradually reduced as the number of ADT cycles increased. The differences in the kinetics for the redox processes would be differences in the degradation mechanism of these cathode electrocatalysts

Protracted Relaxation Dynamics of Lithium Heterogeneity in Solid-State Battery Electrodes

The lithium (Li) heterogeneity formed in the composite electrodes has a significant impact on the performance of solid-state batteries (SSBs). Whereas the influence of various factors on the Li heterogeneity, such as (dis)charge currents, ionic and/or electronic conductivity of the constituent materials, and interfacial charge transfer kinetics, is extensively studied, the influence of the relaxation on the Li heterogeneity in SSB electrodes is largely unexplored, despite its unignorable impact on the battery performance. Here, we performed a three-dimensional operando evaluation of the relaxation dynamics of the electrode-scale Li heterogeneity in a composite SSB electrode under open-circuit conditions after charging using the computed tomography combined with X-ray absorption near-edge structure spectroscopy (CT-XANES). In contrast to the electrode for the liquid-based Li-ion batteries, the Li heterogeneity formed in the composite SSB electrode during charging was not fully relaxed, even after a long open-circuit hold, leaving both higher and lower Li content regions. Such protracted relaxation dynamics in the composite SSB electrode may be due to the high interfacial resistance between active material particles as well as between active material and solid electrolyte particles and is potentially an essential issue for SSBs. This work demonstrated that our CT-XANES technique can three-dimensionally resolve the relaxation dynamics of Li heterogeneity within SSB electrodes, which has only been analyzed indirectly by conventional electrochemical methods such as electrochemical impedance spectroscopy. Our technique can be a valuable tool for identifying detrimental factors affecting the battery performance, ultimately contributing to the development of high-performance SSBs

Operando Time-Resolved X-ray Absorption Fine Structure Study for Surface Events on a Pt₃Co/C Cathode Catalyst in a Polymer Electrolyte Fuel Cell during Voltage-Operating Processes

The structural kinetics of surface events on a Pt₃Co/C cathode catalyst in a polymer electrolyte fuel cell (PEFC) was investigated by operando time-resolved X-ray absorption fine structure (XAFS) with a time resolution of 500 ms. The rate constants of electrochemical reactions, the changes in charge density on Pt, and the changes in the local coordination structures of the Pt₃Co alloy catalyst in the PEFC were successfully evaluated during fuel-cell voltage-operating processes. Significant time lags were observed between the electrochemical reactions and the structural changes in the Pt₃Co alloy catalyst. The rate constants of all the surface events on the Pt₃Co/C catalyst were significantly higher than those on the Pt/C catalyst, suggesting the advantageous behaviors (cell performance and catalyst durability) on the Pt₃Co alloy cathode catalyst