Low‐Coordinated Single‐Atom Catalysts Modulated by Metal Ionic Liquids for Efficient CO₂ Electroreduction

Abstract Modulating the coordination environment of single‐atom catalysts (SACs) is an attractive approach for maximizing the catalytic activity of single‐atom centers. Currently, the synthesis of low‐coordinated SACs is mainly confined to increasing the pyrolysis temperature (≥900 °C) to control C─N volatile fragments. Herein, a novel and universal strategy for the low‐coordinated SACs modulation is presented using transition metal (e.g., Ni, Co, Zn) ionic liquid precursors under relatively mild temperature of 600 °C, which regulates the L‐shell electronic structure and decreases nearly 50% electrophilic reactivity by ionization of 4‐position N atom, thereby orienting synthesis of the SACs with metal‐N3 centers. The Ni‐N3 SACs exhibit exceptional CO₂ electroreduction performance of 99.7% CO Faraday efficiency with an ultra‐high CO partial current density of 467.55 mA·cm⁻² as well as a CO production rate up to 10417.51 µmol·h⁻¹·cm⁻² in flow cell. The superior catalytic activity achieves over twofold increase compared with the Ni‐N4 SACs prepared by non‐metal ionic liquid precursors due to the lower free energy of the key intermediate *COOH and the stronger adsorption energy.