Electroreduction of CO 2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

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

doi:10.1021/acscentsci.7b00160

Title: Electroreduction of CO ₂ Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

Journal Article · Wed Jul 26 00:00:00 EDT 2017 · ACS Central Science

DOI:https://doi.org/10.1021/acscentsci.7b00160· OSTI ID:1372709

Wu, Yueshen ^[1]; Jiang, Jianbing ^[1]; Weng, Zhe ^[1]; Wang, Maoyu ^[2]; Broere, Daniël L. J. ^[3]; Zhong, Yiren ^[1];

^[1];

^[2];

^[1]

Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States; Energy Sciences Institute, Yale University, West Haven, Connecticut 06516, United States
School of Chemical, Biological, and Environmental Engineering, Oregon State University, Corvallis, Oregon 97331, United States
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States

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.

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Research Organization:: Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF); American Chemical Society Petroleum Research Fund; Institute of International Education (IIE); TomKat Foundation; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division and Advanced Photon Source; Dupont Research and Development, Wilmington, DE (United States). DuPont Experimental Station; Northwestern Univ., Evanston, IL (United States); Oregon State Univ., Corvallis, OR (United States); Netherlands Organization for Scientific Research (NWO)

Grant/Contract Number:: FG02-07ER15909; CHE-1651717; AC02-06CH11357

OSTI ID:: 1372709

Alternate ID(s):: OSTI ID: 1423563

Journal Information:: ACS Central Science, Journal Name: ACS Central Science Vol. 3 Journal Issue: 8; ISSN 2374-7943

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 148 works

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Title: Electroreduction of CO ₂ Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center