Abstract

The development of atomically precise dinuclear heterogeneous catalysts is promising to achieve efficient catalytic performance and is also helpful to the atomic-level understanding on the synergy mechanism under reaction conditions. Here, we report a Ni2(dppm)2Cl3 dinuclear-cluster-derived strategy to a uniform atomically precise Ni2 site, consisting of two Ni1–N4 moieties shared with two nitrogen atoms, anchored on a N-doped carbon. By using operando synchrotron X-ray absorption spectroscopy, we identify the dynamically catalytic dinuclear Ni2 structure under electrochemical CO2 reduction reaction, revealing an oxygen-bridge adsorption on the Ni2–N6 site to form an O–Ni2–N6 structure with enhanced Ni–Ni interaction. Theoretical simulations demonstrate that the key O–Ni2–N6 structure can significantly lower the energy barrier for CO2 activation. As a result, the dinuclear Ni2 catalyst exhibits >94% Faradaic efficiency for efficient carbon monoxide production. This work provides bottom-up target synthesis approaches and evidences the identity of dinuclear sites active toward catalytic reactions.