Dramatic differences in carbon dioxide adsorption and initial steps of reduction between silver and copper
Abstract
Converting carbon dioxide (CO_2) into liquid fuels and synthesis gas is a world-wide priority. But there is no experimental information on the initial atomic level events for CO_2 electroreduction on the metal catalysts to provide the basis for developing improved catalysts. Here we combine ambient pressure X-ray photoelectron spectroscopy with quantum mechanics to examine the processes as Ag is exposed to CO_2 both alone and in the presence of H_2O at 298 K. We find that CO_2 reacts with surface O on Ag to form a chemisorbed species (O = CO_2^(δ−)). Adding H_2O and CO_2 then leads to up to four water attaching on O = CO_2^(δ−) and two water attaching on chemisorbed (b-)CO_2. On Ag we find a much more favorable mechanism involving the O = CO_2^(δ−) compared to that involving b-CO_2 on Cu. Each metal surface modifies the gas-catalyst interactions, providing a basis for tuning CO_2 adsorption behavior to facilitate selective product formations.
Additional Information
© The Author(s) 2019. Open Access - This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. Received 25 August 2018. Accepted 27 March 2019. Published 23 April 2019. This work was supported through the Office of Science, Office of Basic Energy Science (BES), of the US Department of Energy (DOE) under Award DE-SC0004993 to the Joint Center for Artificial Photosynthesis, DOE Energy Innovation Hubs. The Advanced Light Source is supported by the Director, Office of Science, Office of BES, of the US DOE under Contract DE-AC02-05CH11231. H.Y. and H.S. gratefully acknowledge China Scholarship Council (CSC, No. 201608320161 and No. 201706340112) for financial support. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number ACI-1548562. Y.Y. and E.J.C. were partially supported by an Early Career Award in the Condensed Phase and Interfacial Molecular Science Program, in the Chemical Sciences Geosciences and Biosciences Division of the Office of Basic Energy Sciences of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. These authors contributed equally: Yifan Ye, Hao Yang, Jin Qian. Author Contributions: Y.Y., J.Y., W.A.G. III and E.J.C. designed the experiments. Y.Y., H.S., K.J.L. and E.J.C. performed the APXPS experiments. H.Y., J.Q., T.C. and H.X. conducted the theoretical computations. Y.Y., H.Y., J.Q., J.Y., W.A.G. III and E.J.C. analyzed the data and wrote the manuscript. All authors contributed to the overall scientific interpretation and edited the manuscript. Data availability: The data that support the findings of this study are available from the corresponding authors upon request. The authors declare no competing interests. Journal peer review information: Nature communication would like to thank Aravind Asthagiri and other anonymous reviewers for their contribution to the peer review of this work. Peer review reports are available.Attached Files
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Supplemental Material - 41467_2019_9846_MOESM1_ESM.pdf
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Additional details
- PMCID
- PMC6478877
- Eprint ID
- 94892
- Resolver ID
- CaltechAUTHORS:20190423-101937653
- DE-SC0004993
- Department of Energy (DOE)
- DE-AC02-05CH11231
- Department of Energy (DOE)
- 201608320161
- China Scholarship Council
- 201706340112
- China Scholarship Council
- ACI-1548562
- NSF
- Created
-
2019-04-23Created from EPrint's datestamp field
- Updated
-
2022-03-01Created from EPrint's last_modified field
- Caltech groups
- JCAP
- Other Numbering System Name
- WAG
- Other Numbering System Identifier
- 1333