Electroreduction of CO2 Catalyzed by a Heterogenized Zn-Porphyrin Complex with a Redox-Innocent Metal Center

Yueshen Wu, Jianbing Jiang, Zhe Weng, Maoyu Wang, Daniël L.J. Broere, Yiren Zhong, Gary W Brudvig, Zhenxing Feng, Hailiang Wang

Research output: Contribution to journalArticle

63 Citations (Scopus)

Abstract

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO2 reduction. Here we report a heterogenized zinc-porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site-1 s-1 and a Faradaic efficiency as high as 95% for CO2 electroreduction to CO at 1.7 V vs the standard hydrogen electrode in an organic/water mixed electrolyte. While the Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc-porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO2. This represents the first example of a transition-metal complex for CO2 electroreduction catalysis with its metal center being redox-innocent under working conditions.

Original languageEnglish
Pages (from-to)847-852
Number of pages6
JournalACS Central Science
Volume3
Issue number8
DOIs
Publication statusPublished - Aug 23 2017

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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