Electrochemical CO2 Reduction to Hydrocarbons on a Heterogeneous Molecular Cu Catalyst in Aqueous Solution.
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.
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.|Energy Sciences Institute, Yale University , West Haven, Connecticut 06516, United States.
Zhe
Z
Weng
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.|Energy Sciences Institute, Yale University , West Haven, Connecticut 06516, United States.
Jianbing
J
Jiang
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.|Energy Sciences Institute, Yale University , West Haven, Connecticut 06516, United States.
Yueshen
Y
Wu
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.|Energy Sciences Institute, Yale University , West Haven, Connecticut 06516, United States.
Zishan
Z
Wu
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.|Energy Sciences Institute, Yale University , West Haven, Connecticut 06516, United States.|Department of Chemistry, Nankai University , Tianjin 300071, The People's Republic of China.
Xiaoting
X
Guo
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.|Energy Sciences Institute, Yale University , West Haven, Connecticut 06516, United States.
Kelly L
KL
Materna
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.|Energy Sciences Institute, Yale University , West Haven, Connecticut 06516, United States.
Wen
W
Liu
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.|Energy Sciences Institute, Yale University , West Haven, Connecticut 06516, United States.
Victor S
VS
Batista
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.|Energy Sciences Institute, Yale University , West Haven, Connecticut 06516, United States.
Gary W
GW
Brudvig
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.|Energy Sciences Institute, Yale University , West Haven, Connecticut 06516, United States.
Hailiang
H
Wang