TY - JOUR
T1 - Binding Site Diversity Promotes CO2 Electroreduction to Ethanol
AU - Li, Yuguang C.
AU - Wang, Ziyun
AU - Yuan, Tiange
AU - Nam, Dae Hyun
AU - Luo, Mingchuan
AU - Wicks, Joshua
AU - Chen, Bin
AU - Li, Jun
AU - Li, Fengwang
AU - De Arquer, F. Pelayo García
AU - Wang, Ying
AU - Dinh, Cao Thang
AU - Voznyy, Oleksandr
AU - Sinton, David
AU - Sargent, Edward H.
N1 - Funding Information:
The authors would like to acknowledge funding supporting from Suncor Energy, the Ontario Research fund, and the Natural Sciences and Engineering Research Council (NSERC). All DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform (SOSCIP). SOSCIP is funded by the Federal Economic Development Agency of Southern Ontario, the Province of Ontario, IBM Canada, Ontario Centres of Excellence, Mitacs and 15 Ontario academic member institutions. This research was enabled inpart by support provided by Compute Ontario and Compute Canada. This research used synchrotron resources of the Advanced Photon Source (APS), an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. The authors thank Dr. T. P. Wu, Dr. Z. Finfrock, Dr. G. Sterbinsky, and Dr. L. Ma for technical support at the 9BM beamline of the Advanced Photon Source. D.S. acknowledges the NSERC E.W.R. Steacie Memorial Fellowship. J.L. acknowledges the Banting Postdoctoral Fellowships program.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/5/29
Y1 - 2019/5/29
N2 - The electrochemical reduction of CO2 has seen many record-setting advances in C2 productivity in recent years. However, the selectivity for ethanol, a globally significant commodity chemical, is still low compared to the selectivity for products such as ethylene. Here we introduce diverse binding sites to a Cu catalyst, an approach that destabilizes the ethylene reaction intermediates and thereby promotes ethanol production. We develop a bimetallic Ag/Cu catalyst that implements the proposed design toward an improved ethanol catalyst. It achieves a record Faradaic efficiency of 41% toward ethanol at 250 mA/cm2 and -0.67 V vs RHE, leading to a cathodic-side (half-cell) energy efficiency of 24.7%. The new catalysts exhibit an in situ Raman spectrum, in the region associated with CO stretching, that is much broader than that of pure Cu controls, a finding we account for via the diversity of binding configurations. This physical picture, involving multisite binding, accounts for the enhanced ethanol production for bimetallic catalysts, and presents a framework to design multimetallic catalysts to control reaction paths in CO2 reductions toward desired products.
AB - The electrochemical reduction of CO2 has seen many record-setting advances in C2 productivity in recent years. However, the selectivity for ethanol, a globally significant commodity chemical, is still low compared to the selectivity for products such as ethylene. Here we introduce diverse binding sites to a Cu catalyst, an approach that destabilizes the ethylene reaction intermediates and thereby promotes ethanol production. We develop a bimetallic Ag/Cu catalyst that implements the proposed design toward an improved ethanol catalyst. It achieves a record Faradaic efficiency of 41% toward ethanol at 250 mA/cm2 and -0.67 V vs RHE, leading to a cathodic-side (half-cell) energy efficiency of 24.7%. The new catalysts exhibit an in situ Raman spectrum, in the region associated with CO stretching, that is much broader than that of pure Cu controls, a finding we account for via the diversity of binding configurations. This physical picture, involving multisite binding, accounts for the enhanced ethanol production for bimetallic catalysts, and presents a framework to design multimetallic catalysts to control reaction paths in CO2 reductions toward desired products.
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U2 - 10.1021/jacs.9b02945
DO - 10.1021/jacs.9b02945
M3 - Article
C2 - 31067857
AN - SCOPUS:85066873133
SN - 0002-7863
VL - 141
SP - 8584
EP - 8591
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 21
ER -