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

Abstract

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO 2 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 CO 2 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 CO 2 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 CO 2. This represents the first example of a transition-metal complex for CO 2 electroreduction catalysis with its metal center being redox-innocent under working conditions.

Authors:
 [1];  [1];  [1];  [2];  [3];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States). Dept. of Chemistry and Energy Science Inst.
  2. Oregon State Univ., Corvallis, OR (United States). School of Chemical, Biological, and Environmental Engineering
  3. Yale Univ., New Haven, CT (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & 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)
OSTI Identifier:
1372709
Alternate Identifier(s):
OSTI ID: 1423563
Grant/Contract Number:  
FG02-07ER15909; CHE-1651717; AC02-06CH11357
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 3; Journal Issue: 8; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wu, Yueshen, Jiang, Jianbing, Weng, Zhe, Wang, Maoyu, Broere, Daniël L. J., Zhong, Yiren, Brudvig, Gary W., Feng, Zhenxing, and Wang, Hailiang. Electroreduction of CO 2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center. United States: N. p., 2017. Web. doi:10.1021/acscentsci.7b00160.
Wu, Yueshen, Jiang, Jianbing, Weng, Zhe, Wang, Maoyu, Broere, Daniël L. J., Zhong, Yiren, Brudvig, Gary W., Feng, Zhenxing, & Wang, Hailiang. Electroreduction of CO 2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center. United States. doi:10.1021/acscentsci.7b00160.
Wu, Yueshen, Jiang, Jianbing, Weng, Zhe, Wang, Maoyu, Broere, Daniël L. J., Zhong, Yiren, Brudvig, Gary W., Feng, Zhenxing, and Wang, Hailiang. Wed . "Electroreduction of CO 2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center". United States. doi:10.1021/acscentsci.7b00160.
@article{osti_1372709,
title = {Electroreduction of CO 2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center},
author = {Wu, Yueshen and Jiang, Jianbing and Weng, Zhe and Wang, Maoyu and Broere, Daniël L. J. and Zhong, Yiren and Brudvig, Gary W. and Feng, Zhenxing and Wang, Hailiang},
abstractNote = {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.},
doi = {10.1021/acscentsci.7b00160},
journal = {ACS Central Science},
issn = {2374-7943},
number = 8,
volume = 3,
place = {United States},
year = {2017},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acscentsci.7b00160

Citation Metrics:
Cited by: 24 works
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Figures / Tables:

Figure 1 Figure 1: (A) The chemical structures of the Zn-porphyrin complex PorZn and its metal-free precursor H2Por. (B) SEM image of the porous coating layer on the carbon fiber paper. (C) SEM image of PorZn deposited on carbon fiber paper. (D) EDS map of Zn for the area in panel C.

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Works referencing / citing this record:

Electrocatalytic CO 2 reduction with nickel complexes supported by tunable bipyridyl-N-heterocyclic carbene donors: understanding redox-active macrocycles
journal, January 2018

  • Su, Xiaojun; McCardle, Kaitlin M.; Panetier, Julien A.
  • Chemical Communications, Vol. 54, Issue 27
  • DOI: 10.1039/c8cc00266e

Electrocatalytic hydrogen evolution with gallium hydride and ligand-centered reduction
journal, January 2019

  • Wang, Ni; Lei, Haitao; Zhang, Zongyao
  • Chemical Science, Vol. 10, Issue 8
  • DOI: 10.1039/c8sc05247f

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.