Oriented electron transmission in polyoxometalate-metalloporphyrin organic framework for highly selective electroreduction of CO<sub>2</sub>.

Wang, Yi-Rong; Huang, Qing; He, Chun-Ting; Chen, Yifa; Liu, Jiang; Shen, Feng-Cui; Lan, Ya-Qian · Nat Commun · 2018

basic_science · Level V

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Abstract

The design of highly stable, selective and efficient electrocatalysts for CO<sub>2</sub> 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<sub>8</sub><sup>V</sup>Mo<sub>4</sub><sup>VI</sup>O<sub>40</sub>Zn<sub>4</sub>} 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<sub>2</sub> 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<sup>-1</sup> and excellent catalysis stability ( > 36 h).