Ligand-Controlled Engineering of Cu–H Active Sites on Cu25 Hydride Nanoclusters for Efficient CO2 Electroreduction

Abstract

Atomic-level control of catalytic selectivity is critical to nanocatalyst design. Here, we report two structurally defined Cu hydride nanoclusters, [Cu25H22(p-FPh3P)12]+ and [Cu25H10(2,4-F2PhS)18]3−, with distinct hydride contents that govern active-site exposure and CO2 electroreduction selectivity. Phosphine ligand dissociation in Cu25H22-P exposed Cu–H sites and favored C2H4 formation, whereas intrinsically exposed Cu–S sites in Cu25H10-S promoted CH4 production. These findings establish hydride ligands as key regulators of active-site structure and product selectivity in Cu nanoclusters.