Investigating the Diversity of Coordination Environments around Pt Atoms

Abstract

AbstractModulating the local coordination environment of catalysts is of overriding importance to control reactivity, but systematic investigation of catalytic active sites with different coordination environments remains elusive. Here, a new strategy is provided to investigate the coordination environment of the catalytic center. Pt atoms, a known catalytic center, were selected to examine the effect of the coordination environment on the electro‐catalytic hydrogen evolution reaction (HER), a well‐studied system. Rather than alter the catalytic metal center as reported in previous work, “surrounding atoms” were tuned to modify the coordination environment around the Pt active center. A clear trend between HER activity and coordination environments with different neighboring atoms, was observed in this work. Based on experimental results, DFT calculations analyzed all coordinated patterns with respect to electronic structures and geometric transformations, giving a full “map” of the relationship between the coordination environments around Pt atoms and their catalytic performances. Such coordination environment engineering could be widely used to screen new catalysts for other conversions, and also provide a novel method for investigating the fundamental chemistry of active sites in catalysis.