Tracking a Common Surface-Bound Intermediate During CO₂-to-Fuels Catalysis
Rational design of selective CO₂-to-fuels electrocatalysts requires direct knowledge of the electrode surface structure during turnover. Metallic Cu is the most versatile CO₂ -to-fuels catalyst, capable of generating a wide array of value-added products, including methane, ethylene, and ethanol. All...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
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American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/113632 https://orcid.org/0000-0001-9519-7907 https://orcid.org/0000-0003-1016-3420 |
| _version_ | 1811073567396200448 |
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| author | Liu, Can Peng, Qiling Yaguchi, Momo Motobayashi, Kenta Ye, Shen Osawa, Masatoshi Wuttig, Anna Hendon, Christopher H Surendranath, Yogesh |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Liu, Can Peng, Qiling Yaguchi, Momo Motobayashi, Kenta Ye, Shen Osawa, Masatoshi Wuttig, Anna Hendon, Christopher H Surendranath, Yogesh |
| author_sort | Liu, Can |
| collection | MIT |
| description | Rational design of selective CO₂-to-fuels electrocatalysts requires direct knowledge of the electrode surface structure during turnover. Metallic Cu is the most versatile CO₂ -to-fuels catalyst, capable of generating a wide array of value-added products, including methane, ethylene, and ethanol. All of these products are postulated to form via a common surface-bound CO intermediate. Therefore, the kinetics and thermodynamics of CO adsorption to Cu play a central role in determining fuel-formation selectivity and efficiency, highlighting the need for direct observation of CO surface binding equilibria under catalytic conditions. Here, we synthesize nanostructured Cu films adhered to IR-transparent Si prisms, and we find that these Cu surfaces enhance IR absorption of bound molecules. Using these films as electrodes, we examine Cu-catalyzed CO₂ reduction in situ via IR spectroelectrochemistry. We observe that Cu surfaces bind electrogenerated CO, derived from CO₂, beginning at -0.60 V vs RHE with increasing surface population at more negative potentials. Adsorbed CO is in dynamic equilibrium with dissolved 13 CO and exchanges rapidly under catalytic conditions. The CO adsorption profiles are pH independent, but adsorbed CO species undergo a reversible transformation on the surface in modestly alkaline electrolytes. These studies establish the potential, concentration, and pH dependencies of the CO surface population on Cu, which serve to maintain a pool of this vital intermediate primed for further reduction to higher order fuel products. |
| first_indexed | 2024-09-23T09:35:01Z |
| format | Article |
| id | mit-1721.1/113632 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T09:35:01Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1136322022-09-26T12:27:04Z Tracking a Common Surface-Bound Intermediate During CO₂-to-Fuels Catalysis Liu, Can Peng, Qiling Yaguchi, Momo Motobayashi, Kenta Ye, Shen Osawa, Masatoshi Wuttig, Anna Hendon, Christopher H Surendranath, Yogesh Massachusetts Institute of Technology. Department of Chemistry Wuttig, Anna Hendon, Christopher H Surendranath, Yogesh Rational design of selective CO₂-to-fuels electrocatalysts requires direct knowledge of the electrode surface structure during turnover. Metallic Cu is the most versatile CO₂ -to-fuels catalyst, capable of generating a wide array of value-added products, including methane, ethylene, and ethanol. All of these products are postulated to form via a common surface-bound CO intermediate. Therefore, the kinetics and thermodynamics of CO adsorption to Cu play a central role in determining fuel-formation selectivity and efficiency, highlighting the need for direct observation of CO surface binding equilibria under catalytic conditions. Here, we synthesize nanostructured Cu films adhered to IR-transparent Si prisms, and we find that these Cu surfaces enhance IR absorption of bound molecules. Using these films as electrodes, we examine Cu-catalyzed CO₂ reduction in situ via IR spectroelectrochemistry. We observe that Cu surfaces bind electrogenerated CO, derived from CO₂, beginning at -0.60 V vs RHE with increasing surface population at more negative potentials. Adsorbed CO is in dynamic equilibrium with dissolved 13 CO and exchanges rapidly under catalytic conditions. The CO adsorption profiles are pH independent, but adsorbed CO species undergo a reversible transformation on the surface in modestly alkaline electrolytes. These studies establish the potential, concentration, and pH dependencies of the CO surface population on Cu, which serve to maintain a pool of this vital intermediate primed for further reduction to higher order fuel products. United States. Air Force Office of Scientific Research (Award FA9550-15-1-0135) 2018-02-13T18:40:56Z 2018-02-13T18:40:56Z 2018-02-13 2018-02-08T16:46:41Z Article http://purl.org/eprint/type/JournalArticle 2374-7943 2374-7951 http://hdl.handle.net/1721.1/113632 Wuttig, Anna et al. “Tracking a Common Surface-Bound Intermediate During CO₂-to-Fuels Catalysis.” ACS Central Science 2, 8 (August 2016): 522–528 © 2016 American Chemical Society https://orcid.org/0000-0001-9519-7907 https://orcid.org/0000-0003-1016-3420 http://dx.doi.org/10.1021/ACSCENTSCI.6B00155 ACS Central Science Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Liu, Can Peng, Qiling Yaguchi, Momo Motobayashi, Kenta Ye, Shen Osawa, Masatoshi Wuttig, Anna Hendon, Christopher H Surendranath, Yogesh Tracking a Common Surface-Bound Intermediate During CO₂-to-Fuels Catalysis |
| title | Tracking a Common Surface-Bound Intermediate During CO₂-to-Fuels Catalysis |
| title_full | Tracking a Common Surface-Bound Intermediate During CO₂-to-Fuels Catalysis |
| title_fullStr | Tracking a Common Surface-Bound Intermediate During CO₂-to-Fuels Catalysis |
| title_full_unstemmed | Tracking a Common Surface-Bound Intermediate During CO₂-to-Fuels Catalysis |
| title_short | Tracking a Common Surface-Bound Intermediate During CO₂-to-Fuels Catalysis |
| title_sort | tracking a common surface bound intermediate during co₂ to fuels catalysis |
| url | http://hdl.handle.net/1721.1/113632 https://orcid.org/0000-0001-9519-7907 https://orcid.org/0000-0003-1016-3420 |
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