Imaging Interface and Particle Size Effects by In Situ Correlative Microscopy of a Catalytic Reaction.

Abstract

The catalytic behavior of Rh particles supported by three different materials (Rh, Au, and ZrO2) in H2 oxidation has been studied in situ by correlative photoemission electron microscopy (PEEM) and scanning photoemission electron microscopy (SPEM). Kinetic transitions between the inactive and active steady states were monitored, and self-sustaining oscillations on supported Rh particles were observed. Catalytic performance differed depending on the support and Rh particle size. Oscillations varied from particle size-independent (Rh/Rh) via size-dependent (Rh/ZrO2) to fully inhibited (Rh/Au). For Rh/Au, the formation of a surface alloy induced such effects, whereas for Rh/ZrO2, the formation of substoichiometric Zr oxides on the Rh surface, enhanced oxygen bonding, Rh-oxidation, and hydrogen spillover onto the ZrO2 support were held responsible. The experimental observations were complemented by micro-kinetic simulations, based on variations of hydrogen adsorption and oxygen binding. The results demonstrate how correlative in situ surface microscopy enables linking of the local structure, composition, and catalytic performance.