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

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 electroreduction (eCORR) by comparing monogold-doped AuCu and homocopper Cu NCs protected by triphenylphosphine or/and tris(4-fluorophenyl)phosphine. Catalytic results revealed that the electronic distribution of Cu 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 eCORR. Overall, this work will provide guidance for the rational design of the copper-based catalysts in the eCORR.