Enhanced CO2 Electroreduction by Stabilizing *COOH on Ni Single Atoms via Short‐ and Long‐Range Electronic Modulation

Abstract Ni single‐atoms (SAs) are active for electrocatalytic CO 2 reduction reaction (CO 2 RR) to CO, but their performance still needs to be further improved for practical implementation. Herein, a strategy of “short‐ and long‐range modulation” is reported to synergistically modulate the electronic structure of Ni SAs by constructing Ni nanoparticles (NPs) integrated with N, P‐coordinated Ni SAs on N‐doped carbon supports (Ni‐P 1 N 3 /Ni NPs @NC). Experiments and theoretical calculations reveal that both the short‐range modulation involving Ni–P coordination and the long‐range modulation by Ni NPs collectively enhance the electron localization around Ni SAs, thus increasing the binding strength for the key * COOH intermediate. This results in an improved CO 2 RR performance of Ni SAs by lowering the energy barrier. Ni‐P 1 N 3 /Ni NPs @NC exhibits a Faradaic efficiency for CO exceeding 99.0% across a wide potential range from −0.5 to −1.1 V versus reversible hydrogen electrode (vs RHE), with the highest partial current density for CO of −544 mA cm −2 at −1.1 V vs RHE.