Near‐ and Long‐Range Electronic Modulation of Single Metal Sites to Boost CO 2 Electrocatalytic Reduction

Tuning the electronic structure of the active center is effective to improve the intrinsic activity of single‐atom catalysts but the realization of precise regulation remains challenging. Herein, a strategy of “synergistically near‐ and long‐range regulation” is reported to effectively modulate the electronic structure of single‐atom sites. ZnN 4 sites decorated with axial sulfur ligand in the first coordination and surrounded phosphorus atoms in the carbon matrix are successfully constructed in the hollow carbon supports (ZnN 4 S 1 /P‐HC). ZnN 4 S 1 /P‐HC exhibits excellent performance for CO 2 reduction reaction (CO 2 RR) with a Faraday efficiency of CO close to 100%. The coupling of the CO 2 RR with thermodynamically favorable hydrazine oxidation reaction to replace oxygen evolution reaction in a two‐electrode electrolyzer can greatly lower the cell voltage by 0.92 V at a current density of 5 mA cm −2 , theoretically saving 46% of energy consumption. Theoretical calculation reveals that the near‐range regulation with axial thiophene‐S ligand and long‐range regulation with neighboring P atoms can synergistically lead to the increase of electron localization around the Zn sites, which strengthens the adsorption of *COOH intermediate and therefore boosts the CO 2 RR.