Interfacial Field-Driven Proton-Coupled Electron Transfer at Graphite-Conjugated Organic Acids

Robert E. Warburton, Phillips Hutchison, Megan N. Jackson, Michael L. Pegis, Yogesh Surendranath, Sharon Hammes-Schiffer

Research output: Contribution to journalArticlepeer-review

35 Scopus citations

Abstract

Interfacial proton-coupled electron transfer (PCET) reactions are central to the operation of a wide array of energy conversion technologies, but molecular-level insights into interfacial PCET are limited. At carbon surfaces, designer sites for interfacial PCET can be incorporated by conjugating organic acid functional groups to graphite edges though aromatic phenazine linkages. At these graphite-conjugated catalysts (GCCs) bearing organic acid moieties, PCET is driven by complex interfacial electrostatic and field gradients that are difficult to probe experimentally. Herein, the spatially inhomogeneous interfacial electrostatic potentials and electric fields of GCC organic acids are computed as functions of applied potential. The calculated proton-coupled redox potentials for the PCET reactions at the GCC phenazine bridges and organic acid sites are in agreement with cyclic voltammetry measurements for a series of GCC acids. The trends in these redox potentials are explained in terms of the acidity of the molecular analogues and continuous conjugation between the acid and the graphite surface. The calculations illustrate that this conjugation is interrupted in a GCC acetic acid system, providing an explanation for the absence of a cyclic voltammetry peak corresponding to PCET at this acid site. This combined theoretical and experimental study demonstrates the critical role of continuous conjugation and strong electronic coupling between the GCC acid site and the graphite to enable interfacial field-driven PCET at the acid site. Understanding the connection between the atomic structure of the surface and the interfacial electrostatic potentials and fields that govern PCET thermochemistry may guide heterogeneous catalyst design.

Original languageEnglish (US)
Pages (from-to)20855-20864
Number of pages10
JournalJournal of the American Chemical Society
Volume142
Issue number49
DOIs
StatePublished - Dec 9 2020
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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