Abstract
AbstractFine‐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 CO2reduction catalysts in a molecular way. The elaborately introduced functional groups (−F, −H and −OMe) can regulate the valance state of Cuδ+, which is found to be directly scaled with the selectivity of the electrochemical CO2‐to‐CH4conversion. An optimum CH4Faradaic 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 Cuδ+centers adjusted by the electron‐withdrawing group decrease the pKaof adsorbed H2O, promoting the hydrogenation of intermediates toward the CH4production. Our strategy paves the way for precise electronic perturbation of SACs toward efficient electrocatalysis.
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