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CO₂ reduction on pure Cu produces only H₂ after subsurface O is depleted: Theory and experiment

Liu, Guiji and Lee, Michelle and Kwon, Soonho and Zeng, Guosong and Eichhorn, Johanna and Buckley, Aya K. and Toste, F. Dean and Goddard, William A., III and Toma, Francesca M. (2021) CO₂ reduction on pure Cu produces only H₂ after subsurface O is depleted: Theory and experiment. Proceedings of the National Academy of Sciences of the United States of America, 118 (23). Art. No. e2012649118. ISSN 0027-8424. PMCID PMC8201769. https://resolver.caltech.edu/CaltechAUTHORS:20210606-014012159

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Abstract

We elucidate the role of subsurface oxygen on the production of C₂ products from CO₂ reduction over Cu electrocatalysts using the newly developed grand canonical potential kinetics density functional theory method, which predicts that the rate of C₂ production on pure Cu with no O is ∼500 times slower than H₂ evolution. In contrast, starting with Cu₂O, the rate of C₂ production is >5,000 times faster than pure Cu(111) and comparable to H₂ production. To validate these predictions experimentally, we combined time-dependent product detection with multiple characterization techniques to show that ethylene production decreases substantially with time and that a sufficiently prolonged reaction time (up to 20 h) leads only to H₂ evolution with ethylene production ∼1,000 times slower, in agreement with theory. This result shows that maintaining substantial subsurface oxygen is essential for long-term C₂ production with Cu catalysts.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1073/pnas.2012649118DOIArticle
https://www.pnas.org/content/suppl/2021/06/03/2012649118.DCSupplementalPublisherSupplemental Information
ORCID:
AuthorORCID
Liu, Guiji0000-0002-3943-4119
Kwon, Soonho0000-0002-9225-3018
Toste, F. Dean0000-0001-8018-2198
Goddard, William A., III0000-0003-0097-5716
Toma, Francesca M.0000-0003-2332-0798
Alternate Title:CO2 reduction on pure Cu produces only H2 after subsurface O is depleted: Theory and experiment
Additional Information:© 2021 The Author(s). Published under the PNAS license. Edited by Michael L. Klein, Temple University, Philadelphia, PA, and approved April 13, 2021 (received for review June 18, 2020) This study is based on work initiated with funding from the Joint Center for Artificial Photosynthesis, a Department of Energy (DOE) Energy Innovation Hub, supported through the Office of Science of the US DOE under Award DE-SC0004993 and completed with funding from the Liquid Sunlight Alliance (LiSA), which is supported by the US DOE, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award DE-SC0021266. Raman spectroscopy and some of the theoretical calculations were specifically supported by LiSA. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US DOE under Contract No. DE-AC02-05CH11231. These studies used the Extreme Science and Engineering Discovery Environment which is supported by National Science Foundation Grant ACI-1548562. G.L., M.L., and S.K. contributed equally to this work. Author contributions: G.L., M.L., S.K., F.D.T., W.A.G., and F.M.T. designed research; G.L., M.L., S.K., and G.Z. performed research; J.E. and A.K.B. performed preliminary measurements; G.L., M.L., S.K., W.A.G., and F.M.T. analyzed the data; and G.L., M.L., S.K., F.D.T., W.A.G., and F.M.T. wrote the paper. Data Availability. All study data are included in the article and/or SI Appendix. The authors declare no competing interest. This article is a PNAS Direct Submission. This article contains supporting information online at https://www.pnas.org/lookup/suppl/doi:10.1073/pnas.2012649118/-/DCSupplemental.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-SC0021266
Department of Energy (DOE)DE-AC02-05CH11231
NSFACI-1548562
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1466
Issue or Number:23
PubMed Central ID:PMC8201769
Record Number:CaltechAUTHORS:20210606-014012159
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210606-014012159
Official Citation:CO2 reduction on pure Cu produces only H2 after subsurface O is depleted: Theory and experiment Guiji Liu, Michelle Lee, Soonho Kwon, Guosong Zeng, Johanna Eichhorn, Aya K. Buckley, F. Dean Toste, William A. Goddard, Francesca M. Toma Proceedings of the National Academy of Sciences Jun 2021, 118 (23) e2012649118; DOI: 10.1073/pnas.2012649118
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109407
Collection:CaltechAUTHORS
Deposited By: Donna Wrublewski
Deposited On:07 Jun 2021 17:38
Last Modified:02 Sep 2021 22:33

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