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Nitrogen-doped Graphene Oxide Electrocatalysts for the Oxygen Reduction Reaction Joseph Henry Dumont, Ulises Martinez, Kateryna Artyushkova, Geraldine Maxine Purdy, Andrew M Dattelbaum, Piotr Zelenay, Aditya D. Mohite, Plamen Atanassov, and Gautam Gupta ACS Appl. Nano Mater., Just Accepted Manuscript • DOI: 10.1021/acsanm.8b02235 • Publication Date (Web): 01 Feb 2019 Downloaded from http://pubs.acs.org on February 4, 2019
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ACS Applied Nano Materials
Nitrogen-doped Graphene Oxide Electrocatalysts for the Oxygen Reduction Reaction Joseph H. Dumont1,2, Ulises Martinez1, Kateryna Artyushkova2, Geraldine M. Purdy1, Andrew M. Dattelbaum1, Piotr Zelenay1, Aditya Mohite1, Plamen Atanassov2, Gautam Gupta,1,† * 1
Los Alamos National Laboratory, Los Alamos, NM 87545, USA.
2
University of New Mexico, Albuquerque, NM 87131, USA.
KEYWORDS: Oxygen reduction reaction; active sites; graphene; graphene oxide; alkaline ABSTRACT Platinum group metal-free (PGM-free) electrocatalysts for the oxygen reduction reaction (ORR) often exhibit a complex functionalized graphitic structure. Because of this complex structure, limited understanding exists about the design factors for the synthesis of high-performing materials. Graphene, a two-dimensional hexagonal structure of carbon, is amenable to structural and functional group modifications, making it an ideal analog to study crucial properties of more complex graphitic materials utilized as electrocatalysts. In this paper, we report the synthesis of active nitrogen-doped graphene oxide catalysts for the ORR in which their activity and fourelectron selectivity is enhanced using simple solvent and electrochemical treatments. The solvents, chosen based on Hansen’s solubility parameters, drive a substantial change in the morphology of the functionalized graphene materials by i) forming microporous holes in the graphitic sheets that leads to edge
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defects and ii) inducing 3D structure in the graphitic sheets that promote ORR. Additionally, the cycling of these catalysts has highlighted the multiplicity of the active sites, with different durability, leading to a highly selective catalyst over time, with a minimal loss in performance. High ORR activity was demonstrated in an alkaline electrolyte with an onset potential of ~1.1 V and half-wave potential of 0.84 V vs RHE. Furthermore, long-term stability potential cycling showed minimal loss in half-wave potential (
