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Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis

Author(s)
Jackson, Megan; Kaminsky, Corey Jarin; Oh, Seokjoon; Melville, Jonathan F.; Surendranath, Yogesh
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Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/
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Abstract
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.
Date issued
2019-07
URI
https://hdl.handle.net/1721.1/125410
Department
Massachusetts Institute of Technology. Department of Chemistry
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
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)
Version: Final published version
ISSN
0002-7863

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