Oriented electron transmission in polyoxometalate-metalloporphyrin organic framework for highly selective electroreduction of CO2

Abstract The design of highly stable, selective and efficient electrocatalysts for CO 2 reduction reaction is desirable while largely unmet. In this work, a series of precisely designed polyoxometalate-metalloporphyrin organic frameworks are developed. Noted that the integration of {ε-PMo 8 V Mo 4 VI O 40 Zn 4 } cluster and metalloporphyrin endows these polyoxometalate-metalloporphyrin organic frameworks greatly advantages in terms of electron collecting and donating, electron migration and electrocatalytic active component in the CO 2 reduction reaction. Thus-obtained catalysts finally present excellent performances and the mechanisms of catalysis processes are discussed and revealed by density functional theory calculations. Most importantly, Co-PMOF exhibits remarkable faradaic efficiency ( > 94%) over a wide potential range (−0.8 to −1.0 V). Its best faradaic efficiency can reach up to 99% (highest in reported metal-organic frameworks) and it exhibits a high turnover frequency of 1656 h −1 and excellent catalysis stability ( > 36 h).