Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis
The efficient interconversion of electrical and chemical energy requires the intimate coupling of electrons and small-molecule substrates at catalyst active sites. In molecular electrocatalysis, the molecule acts as a redox mediator which typically undergoes oxidation or reduction in a separate step...
| প্রধান লেখক: | , , , , |
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| অন্যান্য লেখক: | |
| বিন্যাস: | প্রবন্ধ |
| ভাষা: | English |
| প্রকাশিত: |
American Chemical Society (ACS)
2020
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| অনলাইন ব্যবহার করুন: | https://hdl.handle.net/1721.1/125410 |
| _version_ | 1826217038447640576 |
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| author | Jackson, Megan Kaminsky, Corey Jarin Oh, Seokjoon Melville, Jonathan F. Surendranath, Yogesh |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Jackson, Megan Kaminsky, Corey Jarin Oh, Seokjoon Melville, Jonathan F. Surendranath, Yogesh |
| author_sort | Jackson, Megan |
| collection | MIT |
| description | The efficient interconversion of electrical and chemical energy requires the intimate coupling of electrons and small-molecule substrates at catalyst active sites. In molecular electrocatalysis, the molecule acts as a redox mediator which typically undergoes oxidation or reduction in a separate step from substrate activation. These mediated pathways introduce a high-energy intermediate, cap the driving force for substrate activation at the reduction potential of the molecule, and impede access to high rates at low overpotentials. Here we show that electronically coupling a molecular hydrogen evolution catalyst to a graphitic electrode eliminates stepwise pathways and forces concerted electron transfer and proton binding. Electrochemical and X-ray absorption spectroscopy data establish that hydrogen evolution catalysis at the graphite-conjugated Rh molecule proceeds without first reducing the metal center. These results have broad implications for the molecular-level design of energy conversion catalysts. |
| first_indexed | 2024-09-23T16:57:05Z |
| format | Article |
| id | mit-1721.1/125410 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T16:57:05Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1254102022-09-29T22:38:01Z Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis Jackson, Megan Kaminsky, Corey Jarin Oh, Seokjoon Melville, Jonathan F. Surendranath, Yogesh Massachusetts Institute of Technology. Department of Chemistry The efficient interconversion of electrical and chemical energy requires the intimate coupling of electrons and small-molecule substrates at catalyst active sites. In molecular electrocatalysis, the molecule acts as a redox mediator which typically undergoes oxidation or reduction in a separate step from substrate activation. These mediated pathways introduce a high-energy intermediate, cap the driving force for substrate activation at the reduction potential of the molecule, and impede access to high rates at low overpotentials. Here we show that electronically coupling a molecular hydrogen evolution catalyst to a graphitic electrode eliminates stepwise pathways and forces concerted electron transfer and proton binding. Electrochemical and X-ray absorption spectroscopy data establish that hydrogen evolution catalysis at the graphite-conjugated Rh molecule proceeds without first reducing the metal center. These results have broad implications for the molecular-level design of energy conversion catalysts. United States. Department of Energy. Office of Science. Basic Energy Sciences. Catalysis Science Program (Award DE-SC0014176) National Science Foundation (U.S.). Graduate Research Fellowship (Grant 1122374) United States. Department of Energy. Office of Basic Energy Sciences (Contract DE-AC02-06CH11357) National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Award DMR-1419807) 2020-05-22T14:14:56Z 2020-05-22T14:14:56Z 2019-07 2020-01-14T13:27:52Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 https://hdl.handle.net/1721.1/125410 Jackson, Megan N. et al. “Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis.” Journal of the American Chemical Society 141 (2019): 14160-14167 © 2019 The Author(s) en 10.1021/JACS.9B04981 Journal of the American Chemical Society Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Jackson, Megan Kaminsky, Corey Jarin Oh, Seokjoon Melville, Jonathan F. Surendranath, Yogesh Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis |
| title | Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis |
| title_full | Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis |
| title_fullStr | Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis |
| title_full_unstemmed | Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis |
| title_short | Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis |
| title_sort | graphite conjugation eliminates redox intermediates in molecular electrocatalysis |
| url | https://hdl.handle.net/1721.1/125410 |
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