Fig. 5: DFT calculation of self-reconstruction of Zn-N4 catalytic site for CO2RR induced by planar chlorination engineering.

a The optimized structures of Zn-N4/CNCl−1, Zn-N4/CNCl-2, Zn-N4/CNCl-3 and Zn-N4/CN models. The brown, light blue, gray and green balls represented C, N, Zn and Cl atoms, respectively. b The comparison of Gibbs energy changes of Zn-N4/CNCl-1, Zn-N4/CNCl-2, Zn-N4/CNCl-3 and Zn-N4/CN models during the protonation of coordinated N atom adjacent to C-Cl bond. c The catalytic pathways for CO2RR on Zn-N4/CNCl-1(H), Zn-N4/CNCl-2(H), Zn-N4/CNCl-3(H) and Zn-N4/CN models. d The schematic illustration of catalytic mechanism on Zn-N4/CNCl models. e The catalytic pathways for HER on different models. f The comparison of UL(CO2)-UL(H2) of Zn-N4/CNCl−1(H), Zn-N4/CNCl-2(H), Zn-N4/CNCl-3(H) and Zn-N4/CN models.