Ligand centered electrocatalytic efficient CO₂ reduction reaction at low overpotential on single-atom Ni regulated molecular catalyst

Electrochemical CO₂ reduction reaction (CO₂RR) into value-added chemicals/fuels is crucial for realizing the sustainable carbon cycle while mitigating the energy crisis. However, it is impeded by the relatively high overpotential and low energy efficiency due to the lack of efficient electrocatalysts. Herein, we develop an isolated single-atom Ni catalyst regulated strategy to activate and stabilize the iron phthalocyanine molecule (Ni SA@FePc) toward a highly efficient CO₂RR process at low overpotential. The well-defined and homogenous catalytic centers with unique structures confer Ni SA@FePc with a significantly enhanced CO₂RR performance compared to single-atom Ni catalyst and FePc molecule and afford the atomic understanding on active sites and catalytic mechanism. As expected, Ni SA@FePc exhibits a high selectivity of more significant Faraday efficiency (≥ 95%) over a wide potential range, a high current density of ~ 252 mA·cm⁻² at low overpotential (390 mV), and excellent long-term stability for CO₂RR to CO. X-ray absorption spectroscopy measurement and theoretical calculation indicate the formation of NiN₄-O₂-FePc heterogeneous structure for Ni SA@FePc. And CO₂RR prefers to occur at the raised N centers of NiN₄-O₂-FePc heterogeneous structure for Ni SA@FePc, which enables facilitated adsorption of *COOH and desorption of CO, and thus accelerated overall reaction kinetics.