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 language | English |
|---|---|
| Pages (from-to) | 847-852 |
| Number of pages | 6 |
| Journal | ACS Central Science |
| Volume | 3 |
| Issue number | 8 |
| DOIs | |
| Publication status | Published - Aug 23 2017 |
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ASJC Scopus subject areas
- Chemistry(all)
- Chemical Engineering(all)
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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 journal › Article
}
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.
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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 -