Abstract
Exploration of heterogeneous molecular catalysts combining the atomic-level tunability of molecular structures and the practical handling advantages of heterogeneous catalysts represents an attractive approach to developing high-performance catalysts for important and challenging chemical reactions such as electrochemical carbon dioxide reduction which holds the promise for converting emissions back to fuels utilizing renewable energy. Thus, far, efficient and selective electroreduction of CO2 to deeply reduced products such as hydrocarbons remains a big challenge. Here, we report a molecular copper-porphyrin complex (copper(II)-5,10,15,20-tetrakis(2,6-dihydroxyphenyl)porphyrin) that can be used as a heterogeneous electrocatalyst with high activity and selectivity for reducing CO2 to hydrocarbons in aqueous media. At -0.976 V vs the reversible hydrogen electrode, the catalyst is able to drive partial current densities of 13.2 and 8.4 mA cm-2 for methane and ethylene production from CO2 reduction, corresponding to turnover frequencies of 4.3 and 1.8 molecules·site-1·s-1 for methane and ethylene, respectively. This represents the highest catalytic activity to date for hydrocarbon production over a molecular CO2 reduction electrocatalyst. The unprecedented catalytic performance is attributed to the built-in hydroxyl groups in the porphyrin structure and the reactivity of the copper(I) metal center.
| Original language | English |
|---|---|
| Pages (from-to) | 8076-8079 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 138 |
| Issue number | 26 |
| DOIs | |
| Publication status | Published - Jul 6 2016 |
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ASJC Scopus subject areas
- Catalysis
- Biochemistry
- Chemistry(all)
- Colloid and Surface Chemistry
Cite this
Electrochemical CO2 Reduction to Hydrocarbons on a Heterogeneous Molecular Cu Catalyst in Aqueous Solution. / Weng, Zhe; Jiang, Jianbing; Wu, Yueshen; Wu, Zishan; Guo, Xiaoting; Materna, Kelly L.; Liu, Wen; Batista, Victor S.; Brudvig, Gary W; Wang, Hailiang.
In: Journal of the American Chemical Society, Vol. 138, No. 26, 06.07.2016, p. 8076-8079.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Electrochemical CO2 Reduction to Hydrocarbons on a Heterogeneous Molecular Cu Catalyst in Aqueous Solution
AU - Weng, Zhe
AU - Jiang, Jianbing
AU - Wu, Yueshen
AU - Wu, Zishan
AU - Guo, Xiaoting
AU - Materna, Kelly L.
AU - Liu, Wen
AU - Batista, Victor S.
AU - Brudvig, Gary W
AU - Wang, Hailiang
PY - 2016/7/6
Y1 - 2016/7/6
N2 - Exploration of heterogeneous molecular catalysts combining the atomic-level tunability of molecular structures and the practical handling advantages of heterogeneous catalysts represents an attractive approach to developing high-performance catalysts for important and challenging chemical reactions such as electrochemical carbon dioxide reduction which holds the promise for converting emissions back to fuels utilizing renewable energy. Thus, far, efficient and selective electroreduction of CO2 to deeply reduced products such as hydrocarbons remains a big challenge. Here, we report a molecular copper-porphyrin complex (copper(II)-5,10,15,20-tetrakis(2,6-dihydroxyphenyl)porphyrin) that can be used as a heterogeneous electrocatalyst with high activity and selectivity for reducing CO2 to hydrocarbons in aqueous media. At -0.976 V vs the reversible hydrogen electrode, the catalyst is able to drive partial current densities of 13.2 and 8.4 mA cm-2 for methane and ethylene production from CO2 reduction, corresponding to turnover frequencies of 4.3 and 1.8 molecules·site-1·s-1 for methane and ethylene, respectively. This represents the highest catalytic activity to date for hydrocarbon production over a molecular CO2 reduction electrocatalyst. The unprecedented catalytic performance is attributed to the built-in hydroxyl groups in the porphyrin structure and the reactivity of the copper(I) metal center.
AB - Exploration of heterogeneous molecular catalysts combining the atomic-level tunability of molecular structures and the practical handling advantages of heterogeneous catalysts represents an attractive approach to developing high-performance catalysts for important and challenging chemical reactions such as electrochemical carbon dioxide reduction which holds the promise for converting emissions back to fuels utilizing renewable energy. Thus, far, efficient and selective electroreduction of CO2 to deeply reduced products such as hydrocarbons remains a big challenge. Here, we report a molecular copper-porphyrin complex (copper(II)-5,10,15,20-tetrakis(2,6-dihydroxyphenyl)porphyrin) that can be used as a heterogeneous electrocatalyst with high activity and selectivity for reducing CO2 to hydrocarbons in aqueous media. At -0.976 V vs the reversible hydrogen electrode, the catalyst is able to drive partial current densities of 13.2 and 8.4 mA cm-2 for methane and ethylene production from CO2 reduction, corresponding to turnover frequencies of 4.3 and 1.8 molecules·site-1·s-1 for methane and ethylene, respectively. This represents the highest catalytic activity to date for hydrocarbon production over a molecular CO2 reduction electrocatalyst. The unprecedented catalytic performance is attributed to the built-in hydroxyl groups in the porphyrin structure and the reactivity of the copper(I) metal center.
UR - http://www.scopus.com/inward/record.url?scp=84978951905&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84978951905&partnerID=8YFLogxK
U2 - 10.1021/jacs.6b04746
DO - 10.1021/jacs.6b04746
M3 - Article
AN - SCOPUS:84978951905
VL - 138
SP - 8076
EP - 8079
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 26
ER -