Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis

Jackson, Megan N.; Kaminsky, Corey J.; Oh, Seokjoon; Melville, Jonathan F.; Surendranath, Yogesh

doi:10.1021/jacs.9b04981

Title: Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis

Journal Article · 29 July 2019 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.9b04981 · OSTI ID:1561558

Jackson, Megan N. ^[1]; Kaminsky, Corey J. ^[2]; Oh, Seokjoon ^[2]; Melville, Jonathan F. ^[2];

^[2]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of California, Berkeley, CA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

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.

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0014176

OSTI ID:: 1561558

Journal Information:: Journal of the American Chemical Society, Vol. 141, Issue 36; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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