Effects of ligand tuning and core doping of atomically precise copper nanoclusters on CO2 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 CO₂ electroreduction (eCO₂RR) by comparing monogold-doped Au₁Cu₂₄ and homocopper Cu₂₅ NCs protected by triphenylphosphine or/and tris(4-fluorophenyl)phosphine. Catalytic results revealed that the electronic distribution of Cu₂₅ 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 eCO₂RR. Overall, this work will provide guidance for the rational design of the copper-based catalysts in the eCO₂RR. Tuning the metal core and ligand environment of atomically precise nanoclusters enables the correlation of structural and electrocatalytic properties at an atomic level. Here, single-atom doping and ligand tuning of atomically precise copper clusters is shown to be an effective route to tuning CO₂ electroreduction activity and selectivity. [ABSTRACT FROM AUTHOR]