Electronic Perturbation of Copper Single-Atom CO₂ Reduction Catalysts in a Molecular Way

Fine-tuning electronic structures of single-atom catalysts (SACs) plays a crucial role in harnessing their catalytic activities, yet challenges remain at a molecular scale in a controlled fashion. By tailoring the structure of graphdiyne (GDY) with electron-withdrawing/-donating groups, we show herein the electronic perturbation of Cu single-atom CO₂ reduction catalysts in a molecular way. The elaborately introduced functional groups (-F, -H and -OMe) can regulate the valance state of Cu^δ+ , which is found to be directly scaled with the selectivity of the electrochemical CO₂ -to-CH₄ conversion. An optimum CH₄ Faradaic efficiency of 72.3 % was achieved over the Cu SAC on the F-substituted GDY. In situ spectroscopic studies and theoretical calculations revealed that the positive Cu^δ+ centers adjusted by the electron-withdrawing group decrease the pK_a of adsorbed H₂ O, promoting the hydrogenation of intermediates toward the CH₄ production. Our strategy paves the way for precise electronic perturbation of SACs toward efficient electrocatalysis.