Manipulating electronic and geometric effects of Pt nanoparticles exerted from Co single atoms in the selective hydrogenation of epichlorohydrin

Abstract

This study demonstrates the separate manipulation of electronic and geometric effects in Pt–Co/C catalysts, where Co single atoms decorate Pt nanoparticles, to solve two issues in ECH selective hydrogenation: dechlorination and ring-opening regioselectivity. We decoupled these effects by synthesizing two model catalysts: Co/C–Pt (for the electronic effect) and Pt/C–Co (for the geometric effect). The electronic effect, characterized by XPS, enhanced the selectivity of 1-chloro-2-propanol from 80.1% to 96.7%. The geometric effect, confirmed by H₂–O₂ titration, drastically improved the yield of the anti-Markovnikov product (3-chloro-1-propanol) from 0.4% to 41.9%. Combined TPD and DFT calculations revealed that the Co atoms tailor the adsorption properties of Pt and the configuration of adsorbed ECH, which is the origin of the enhanced catalytic performance.