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

46 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

Fingerprint

Porphyrins
Metals
Zinc
Electrocatalysts
Carbon Monoxide
Catalysis
Transition metals
Ligands
Coordination Complexes
X ray absorption
Metal complexes
Electrolytes
Cyclic voltammetry
Hydrogen
Electrodes
Catalysts
Oxidation-Reduction
Water
zinc hematoporphyrin

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Electroreduction of CO2 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.

In: ACS Central Science, Vol. 3, No. 8, 23.08.2017, p. 847-852.

Research output: Contribution to journalArticle

Wu, Yueshen ; Jiang, Jianbing ; Weng, Zhe ; Wang, Maoyu ; Broere, Daniël L.J. ; Zhong, Yiren ; Brudvig, Gary W ; Feng, Zhenxing ; Wang, Hailiang. / Electroreduction of CO2 Catalyzed by a Heterogenized Zn-Porphyrin Complex with a Redox-Innocent Metal Center. In: ACS Central Science. 2017 ; Vol. 3, No. 8. pp. 847-852.
@article{4a2adf04cd01408abc70cbfbe80912dd,
title = "Electroreduction of CO2 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 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.",
author = "Yueshen Wu and Jianbing Jiang and Zhe Weng and Maoyu Wang and Broere, {Dani{\"e}l L.J.} and Yiren Zhong and Brudvig, {Gary W} and Zhenxing Feng and Hailiang Wang",
year = "2017",
month = "8",
day = "23",
doi = "10.1021/acscentsci.7b00160",
language = "English",
volume = "3",
pages = "847--852",
journal = "ACS Central Science",
issn = "2374-7943",
publisher = "American Chemical Society",
number = "8",

}

TY - JOUR

T1 - Electroreduction of CO2 Catalyzed by a Heterogenized Zn-Porphyrin Complex with a Redox-Innocent Metal Center

AU - Wu, Yueshen

AU - Jiang, Jianbing

AU - Weng, Zhe

AU - Wang, Maoyu

AU - Broere, Daniël L.J.

AU - Zhong, Yiren

AU - Brudvig, Gary W

AU - Feng, Zhenxing

AU - Wang, Hailiang

PY - 2017/8/23

Y1 - 2017/8/23

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85028037260&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85028037260&partnerID=8YFLogxK

U2 - 10.1021/acscentsci.7b00160

DO - 10.1021/acscentsci.7b00160

M3 - Article

AN - SCOPUS:85028037260

VL - 3

SP - 847

EP - 852

JO - ACS Central Science

JF - ACS Central Science

SN - 2374-7943

IS - 8

ER -