1. Electrochemical CO2 Reduction to Hydrocarbons on a Heterogeneous Molecular Cu Catalyst in Aqueous Solution
- Author
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Gary W. Brudvig, Zhe Weng, Yueshen Wu, Kelly L. Materna, Xiaoting Guo, Victor S. Batista, Jianbing Jiang, Hailiang Wang, Wen Liu, and Zishan Wu
- Subjects
Aqueous solution ,Chemistry ,Catalyst support ,Inorganic chemistry ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Electrocatalyst ,Electrochemistry ,01 natural sciences ,Biochemistry ,Chemical reaction ,Catalysis ,0104 chemical sciences ,Colloid and Surface Chemistry ,Chemical engineering ,Reversible hydrogen electrode ,0210 nano-technology ,Electrochemical reduction of carbon dioxide - 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.
- Published
- 2016