Atomically Precise Dinuclear Site Active toward Electrocatalytic CO2 Reduction

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.