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Bimetallic effects on Zn-Cu electrocatalysts enhance activity and selectivity for the conversion of CO₂ to CO

Wang, Lei and Peng, Hongjie and Lamaison, Sarah and Qi, Zhifu and Koshy, David M. and Stevens, Michaela Burke and Wakerley, David and Zamora Zeledón, José A. and King, Laurie A. and Zhou, Lan and Lai, Yungchieh and Fontecave, Marc and Gregoire, John and Abild-Pedersen, Frank and Jaramillo, Thomas F. and Hahn, Christopher (2021) Bimetallic effects on Zn-Cu electrocatalysts enhance activity and selectivity for the conversion of CO₂ to CO. Chem Catalysis, 1 (3). pp. 663-680. ISSN 2667-1093. https://resolver.caltech.edu/CaltechAUTHORS:20210607-115054455

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Abstract

We report an active zinc-copper (Zn-Cu) bimetallic electrocatalyst for CO₂ reduction to CO, prepared by a facile galvanic procedure. Under moderate overpotentials, Zn-Cu catalysts that are Zn rich exhibit intrinsic activity for CO formation superior to that of pure Zn, Cu, and Ag, the last of which is the state-of-the-art catalyst in CO₂ electrolyzers. Combinatorial experiments involving catalysts prepared by physical vapor deposition reveal trends across the Zn-Cu system, corroborating the high CO selectivity unrivaled by other alloys and intermetallics. Physical and electrochemical characterization and first principles theory reveal that the origin of this synergy in intrinsic activity is an electronic effect from bimetallic Zn-Cu sites that stabilizes the carboxyl intermediate during CO₂ reduction to CO. Furthermore, by integrating Zn-Cu into gas-diffusion electrodes, we demonstrate that bimetallic effects lead to improved electrocatalytic performance at industrially relevant currents. These insights provide catalyst design principles that can guide future development of efficient and earth-abundant CO-producing electrocatalysts.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1016/j.checat.2021.05.006DOIArticle
ORCID:
AuthorORCID
Wang, Lei0000-0002-1931-7767
Stevens, Michaela Burke0000-0003-3584-0600
Zhou, Lan0000-0002-7052-266X
Lai, Yungchieh0000-0001-9392-1447
Gregoire, John0000-0002-2863-5265
Jaramillo, Thomas F.0000-0001-9900-0622
Hahn, Christopher0000-0002-2772-6341
Alternate Title:Bimetallic effects on Zn-Cu electrocatalysts enhance activity and selectivity for the conversion of CO2 to CO
Additional Information:© 2021 Elsevier. Received 26 January 2021, Revised 18 April 2021, Accepted 6 May 2021, Available online 7 June 2021. The galvanic-exchange synthesis, physical and electrochemical characterization, and DFT calculations on Zn-Cu bimetallics are based on work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award DE-SC0004993. Combinatorial high-throughput measurements of sputtered Cu-Zn catalysts are based on work performed by the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award DE-SC0021266. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under Award ECCS-1542152. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract DE-AC02-76SF00515. Additional thanks go to the Stanford NMR Facility. L.W. thanks the Knut and Alice Wallenberg Foundation for financial support and the National University of Singapore and Ministry of Education – Singapore for its financial support through Tier-1 projects with grants R-279-000-622-133 and R-279-000-622-731. Author contributions. Conceptualization, L.W., T.F.J., and C.H.; methodology, L.W., H.P., S.L., Z.Q., D.K., M.B.S., J.A.Z.Z., D.W., L.K., L.Z., and Y.L.; investigation, L.W., H.P., S.L., Z.Q., D.K., M.B.S., J.A.Z.Z., D.W., L.K., L.Z., Y.L., and M.F.; writing – original draft, L.W., H.P., and S.L.; writing – review & editing, L.W., H.P., S.L., Z.Q., D.K., M.B.S., J.A.Z.Z., D.W., L.K., L.Z., Y.L., M.F., J.G., F.A.-P., T.F.J., and C.H.; funding acquisition, J.G., F.A.-P., T.F.J., and C.H.; supervision, J.G., F.A.-P., T.F.J., and C.H. The authors declare no competing interests.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-SC0021266
NSFECCS-1542152
Department of Energy (DOE)DE-AC02-76SF00515
Knut and Alice Wallenberg FoundationUNSPECIFIED
National University of SingaporeUNSPECIFIED
Ministry of Education (Singapore)R-279-000-622-133
Ministry of Education (Singapore)R-279-000-622-731
Subject Keywords:CO2 reduction; CO formation; bimetallic effect; electrocatalysis
Issue or Number:3
Record Number:CaltechAUTHORS:20210607-115054455
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210607-115054455
Official Citation:Lei Wang, Hongjie Peng, Sarah Lamaison, Zhifu Qi, David M. Koshy, Michaela Burke Stevens, David Wakerley, José A. Zamora Zeledón, Laurie A. King, Lan Zhou, Yungchieh Lai, Marc Fontecave, John Gregoire, Frank Abild-Pedersen, Thomas F. Jaramillo, Christopher Hahn, Bimetallic effects on Zn-Cu electrocatalysts enhance activity and selectivity for the conversion of CO2 to CO, Chem Catalysis, Volume 1, Issue 3, 2021, Pages 663-680, ISSN 2667-1093, https://doi.org/10.1016/j.checat.2021.05.006.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109418
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:08 Jun 2021 14:06
Last Modified:20 Aug 2021 17:00

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