Effects of ligand tuning and core doping of atomically precise copper nanoclusters on CO2 electroreduction selectivity

Abstract Atomically precise nanoclusters (NCs) provide opportunities for correlating the structure and electrocatalytic properties at atomic level. Herein, we report the single-atom doping effect and ligand effect on CO 2 electroreduction (eCO 2 RR) by comparing monogold-doped Au 1 Cu 24 and homocopper Cu 25 NCs protected by triphenylphosphine or/and tris(4-fluorophenyl)phosphine. Catalytic results revealed that the electronic distribution of Cu 25 NCs is enormously contracted by doping Au atoms, entitling it to exhibit the unique inhibition of hydrogen evolution reaction. And the inductive effect of ligand strongly favors the formation of formate in eCO 2 RR. Overall, this work will provide guidance for the rational design of the copper-based catalysts in the eCO 2 RR.