Chlorine-Coordinated Unsaturated Ni–N2 Sites for Efficient Electrochemical Carbon Dioxide Reduction

Heteroatom-doping is an effective method for modifying the geometric symmetry of metal–nitrogen–carbon (M–N–C) single-atom catalysts and thereby tuning the electronic structure. Up to now, most of the current reports have concentrated on introducing heteroatoms into the highly symmetrical M–N 4 structure. The coordination-unsaturated M–N 2 structure is more sterically favorable for the insertion of alien atoms to optimize the electronic structure. Herein, a Ni–N 2 catalyst with out-of-plane coordinated chlorine (Cl) atoms (Ni–N 2 Cl/C) is successfully constructed on chlorine-functionalized carbon supports (C–Cl) for an efficient carbon dioxide reduction reaction (CO 2 RR). Density functional theory calculations demonstrate that the prepared Ni–N 2 Cl/C catalyst exhibits a higher capability in balancing COOH* formation and CO* desorption. In addition, in situ Raman spectra confirm that the lower CO binding energy on the Ni–N 2 Cl/C facilitates CO escape, leading to excellent CO 2 RR performance. A high CO Faradaic efficiency (FE CO ) of more than 80% is achieved from −0.6 to −1.2 V versus reversible hydrogen electrode on the Ni–N 2 Cl/C and it exhibits negligible FE CO and current declination over a 40-h stability test. Furthermore, a high turnover frequency (TOF) value of 15 808 h −1 is obtained, which is more than ten times that of Ni–N 2 /C (1476 h −1 ) without coordinated Cl atoms.