Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis
Name
jacs.9b04981.pdf
Description
Published version
Size
1.49 MB
Format
Adobe PDF
Checksum (MD5)
fcd91553040be5333f707202522b8d2b
Author(s)
Jackson, Megan
Kaminsky, Corey Jarin
Oh, Seokjoon
Melville, Jonathan F.
Surendranath, Yogesh
Date Issued
July 2019
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
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Creative Commons Attribution-NonCommercial-NoDerivs License
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DOI of Published Version
https://doi.org/10.1021/JACS.9B04981
