Restructuring dynamics of surface species in bimetallic nanoparticles probed by modulation excitation spectroscopy
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Engineering topics
Publications and source records attributed to Frenkel, Anatoly I. (ORCID:0000000254511207).
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Abstract Single-atom catalysts (SACs) are particularly sensitive to external conditions, complicating the identification of catalytically active species and active sites under in situ or operando conditions. We developed a methodology for tracing the structural evolution of SACs to nanoparticles, identifying the active species and their link to the catalytic activity for the reverse water gas shift (RWGS) reaction. The new method is illustrated by studying structure-activity relationships in two materials containing Pt SACs on ceria nanodomes, supported on either ceria or titania. These materials exhibited distinctly different activities for CO production. Multimodal operando characterization attributed the enhanced activity of the titania-supported catalysts at temperatures below 320 ˚C to the formation of unique Pt sites at the ceria-titania interface capable of forming Pt nanoparticles, the active species for the RWGS reaction. Migration of Pt nanoparticles to titania support was found to be responsible for the deactivation of titania-supported catalysts at elevated temperatures. Tracking the migration of Pt atoms provides a new opportunity to investigate the activation and deactivation of Pt SACs for the RWGS reaction.
Material properties of Ga–Sb binary alloy thin films deposited under ultra-high vacuum conditions were studied for analog phase change memory (PCM) applications. Crystallization of this alloy was shown to occur in the temperature range of 180–264 °C, with activation energy >2.5 eV depending on the composition. X-ray diffraction (XRD) studies showed phase separation upon crystallization into two phases, Ga-doped A7 antimony and cubic zinc-blende GaSb. Synchrotron in situ XRD analysis revealed that crystallization into the A7 phase is accompanied by Ga out-diffusion from the grains. X-ray absorption fine structure studies of the local structure of these alloys demonstrated a bond length decrease with a stable coordination number of 4 upon amorphous-to-crystalline phase transformation. Mushroom cell structures built with Ga–Sb alloys on ø110 nm TiN heater show a phase change material resistance switching behavior with resistance ratio >100 under electrical pulse measurements. TEM and Energy Dispersive Spectroscopy (EDS) studies of the Ga–Sb cells after ∼100 switching cycles revealed that partial SET or intermediate resistance states are attained by the variation of the grain size of the material as well as the Ga content in the A7 phase. A mechanism for a reversible composition control is proposed for analog cell performance. These results indicate that Te-free Ga–Sb binary alloys are potential candidates for analog PCM applications.
Abstract Three-dimensional bicontinuous porous materials formed by dealloying contribute significantly to various applications including catalysis, sensor development and energy storage. This work studies a method of molten salt dealloying via real-time in situ synchrotron three-dimensional X-ray nano-tomography. Quantification of morphological parameters determined that long-range diffusion is the rate-determining step for the dealloying process. The subsequent coarsening rate was primarily surface diffusion controlled, with Rayleigh instability leading to ligament pinch-off and creating isolated bubbles in ligaments, while bulk diffusion leads to a slight densification. Chemical environments characterized by X-ray absorption near edge structure spectroscopic imaging show that molten salt dealloying prevents surface oxidation of the metal. In this work, gaining a fundamental mechanistic understanding of the molten salt dealloying process in forming porous structures provides a nontoxic, tunable dealloying technique and has important implications for molten salt corrosion processes, which is one of the major challenges in molten salt reactors and concentrated solar power plants.
Abstract not provided