Molecular-Level Insights into Oxygen Reduction Catalysis by Graphite-Conjugated Active Sites
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NGCC_Manscript_ACSCat_Final_Resub.pdf
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Author(s)
Ricke, Nathan Darrell
Murray, Alexander T
Shepherd, James J
Welborn, Matthew Gregory
Fukushima, Tomohiro
Van Voorhis, Troy
Surendranath, Yogesh
Date Issued
September 2017
Journal
ACS Catalysis
Publisher
American Chemical Society (ACS)
Citation
Ricke, Nathan D. et al. “Molecular-Level Insights into Oxygen Reduction Catalysis by Graphite-Conjugated Active Sites.” ACS Catalysis 7, 11 (October 2017): 7680–7687 © 2017 American Chemical Society
Version
Author's final manuscript
Abstract
Using a combination of experimental and computational investigations, we assemble a consistent mechanistic model for the oxygen reduction reaction (ORR) at molecularly well-defined graphite-conjugated catalyst (GCC) active sites featuring aryl-pyridinium moieties (N⁺-GCC). ORR catalysis at glassy carbon surfaces modified with N⁺-GCC fragments displays near-first-order dependence in O₂ partial pressure and near-zero-order dependence on electrolyte pH. Tafel analysis suggests an equilibrium one-electron transfer process followed by a rate-limiting chemical step at modest overpotentials that transitions to a rate-limiting electron transfer sequence at higher overpotentials. Finite-cluster computational modeling of the N⁺-GCC active site reveals preferential O₂ adsorption at electrophilic carbons alpha to the pyridinium moiety. Together, the experimental and computational data indicate that ORR proceeds via a proton-decoupled O₂ activation sequence involving either concerted or stepwise electron transfer and adsorption of O₂, which is then followed by a series of electron/proton transfer steps to generate water and turn over the catalytic cycle. The proposed mechanistic model serves as a roadmap for the bottom-up synthesis of highly active N-doped carbon ORR catalysts. Keywords: density functional theory; electrocatalysis; mechanistic studies; N-doped carbon; oxygen reduction
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1021/acscatal.7b03086
