Graphite-Conjugated Acids Reveal a Molecular Framework for Proton-Coupled Electron Transfer at Electrode Surfaces

Jackson, Megan N.; Pegis, Michael L.; Surendranath, Yogesh

doi:10.1021/acscentsci.9b00114

Title: Graphite-Conjugated Acids Reveal a Molecular Framework for Proton-Coupled Electron Transfer at Electrode Surfaces

Journal Article · 01 May 2019 · ACS Central Science

DOI: https://doi.org/10.1021/acscentsci.9b00114 · OSTI ID:1510160

Jackson, Megan N. ^[1];

^[1];

^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry

Proton-coupled electron-transfer (PCET) steps play a key role in energy conversion reactions. Molecular PCET reactions are well-described by “square schemes” in which the overall thermochemistry of the reaction is broken into its constituent proton-transfer and electron-transfer components. Although this description has been essential for understanding molecular PCET, no such framework exists for PCET reactions that take place at electrode surfaces. Herein, we develop a molecular square scheme framework for interfacial PCET by investigating the electrochemistry of molecularly well-defined acid/base sites conjugated to graphitic electrodes. Using cyclic voltammetry, we first demonstrate that, irrespective of the redox properties of the corresponding molecular analogue, proton transfer to graphite-conjugated acid/base sites is coupled to electron transfer. We then show that the thermochemistry of surface PCET events can be described by the pK_a of the molecular analogue and the potential of zero free charge (zero-field reduction potential) of the electrode. Finally, this work provides a general framework for analyzing and predicting the thermochemistry of interfacial PCET reactions.

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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:: 1510160

Alternate ID(s):: OSTI ID: 1515187

Journal Information:: ACS Central Science, Vol. 5, Issue 5; ISSN 2374-7943

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Metal Chalcogenide Nanofilms: Platforms for Mechanistic Studies of Electrocatalysis Falkowski, Joseph M.; Surendranath, Yogesh ACS Catalysis, Vol. 5, Issue 6 https://doi.org/10.1021/acscatal.5b00449	journal	May 2015
A Membrane-Free Neutral pH Formate Fuel Cell Enabled by a Selective Nickel Sulfide Oxygen Reduction Catalyst Yan, Bing; Concannon, Nolan M.; Milshtein, Jarrod D. Angewandte Chemie International Edition, Vol. 56, Issue 26 https://doi.org/10.1002/anie.201702578	journal	May 2017
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