Hybrid CO2 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(Ni8-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 CO2 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_8~(II)clusters to metalloporphyrins under electric fields results in the raised oxidizability of Ni8 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 CO2 electroreduction.
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