Manipulating electronic and geometric effect from Co single atoms to Pt nanoparticles in the selective hydrogenation of Epichlorohydrin

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 electronic effect) and Pt/C-Co (for 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 reveal 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.