Redox‐Active Crystalline Coordination Catalyst for Hybrid Electrocatalytic Methanol Oxidation and CO2 Reduction

Abstract Hybrid CO 2 electroreduction (HCER) is recognized as an important strategy to improve the total value of redox products and energy conversion efficiency. In this work, a coordination catalyst model system (Ni 8 ‐TET with active oxidation sites, Ni‐TPP with active reduction sites and PCN‐601 with redox‐active sites) for HCER was established for the first time. Especially, PCN‐601 can complete both anodic methanol oxidation and cathodic CO 2 reduction with FE HCOOH and FE CO over 90 %. The performance can be further improved with light irradiation (FE nearly 100 %). DFT calculations reveal that the transfer of electrons from Ni II 8 clusters to metalloporphyrins under electric fields results in the raised oxidizability of Ni 8 clusters and the raised reducibility of metalloporphyrin, which then improves the electrocatalytic performance. This work serves as a well‐defined model system and puts forward a new design idea for establishing efficient catalysts for hybrid CO 2 electroreduction.