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Title: Nitrogen-Doped Graphene Oxide Electrocatalysts for the Oxygen Reduction Reaction

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 analogue 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 four-electron selectivity are 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 lead to edge defects and (ii) inducing 3D structure in the graphitic sheets that promotes 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.more » Furthermore, long-term stability potential cycling showed minimal loss in half-wave potential (<3%) in both N 2- and O 2-saturated solutions with improved selectivity toward the four-electron reduction after 10000 cycles. Lastly, the results described in this work provide additional understanding about graphitic electrocatalysts in alkaline media that may be utilized to further enhance the performance of PGM-free ORR electrocatalysts.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [2];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3];  [2]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of New Mexico, Albuquerque, NM (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of New Mexico, Albuquerque, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1495149
Report Number(s):
LA-UR-18-20904
Journal ID: ISSN 2574-0970
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Nano Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 3; Journal ID: ISSN 2574-0970
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Energy Sciences; Material Science; Oxygen reduction reaction; graphene; graphene oxide; alkaline

Citation Formats

Dumont, Joseph H., Martinez, Ulises, Artyushkova, Kateryna, Purdy, Geraldine M., Dattelbaum, Andrew M., Zelenay, Piotr, Mohite, Aditya, Atanassov, Plamen, and Gupta, Gautam. Nitrogen-Doped Graphene Oxide Electrocatalysts for the Oxygen Reduction Reaction. United States: N. p., 2019. Web. doi:10.1021/acsanm.8b02235.
Dumont, Joseph H., Martinez, Ulises, Artyushkova, Kateryna, Purdy, Geraldine M., Dattelbaum, Andrew M., Zelenay, Piotr, Mohite, Aditya, Atanassov, Plamen, & Gupta, Gautam. Nitrogen-Doped Graphene Oxide Electrocatalysts for the Oxygen Reduction Reaction. United States. doi:10.1021/acsanm.8b02235.
Dumont, Joseph H., Martinez, Ulises, Artyushkova, Kateryna, Purdy, Geraldine M., Dattelbaum, Andrew M., Zelenay, Piotr, Mohite, Aditya, Atanassov, Plamen, and Gupta, Gautam. Fri . "Nitrogen-Doped Graphene Oxide Electrocatalysts for the Oxygen Reduction Reaction". United States. doi:10.1021/acsanm.8b02235.
@article{osti_1495149,
title = {Nitrogen-Doped Graphene Oxide Electrocatalysts for the Oxygen Reduction Reaction},
author = {Dumont, Joseph H. and Martinez, Ulises and Artyushkova, Kateryna and Purdy, Geraldine M. and Dattelbaum, Andrew M. and Zelenay, Piotr and Mohite, Aditya and Atanassov, Plamen and Gupta, Gautam},
abstractNote = {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 analogue 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 four-electron selectivity are 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 lead to edge defects and (ii) inducing 3D structure in the graphitic sheets that promotes 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 (<3%) in both N2- and O2-saturated solutions with improved selectivity toward the four-electron reduction after 10000 cycles. Lastly, the results described in this work provide additional understanding about graphitic electrocatalysts in alkaline media that may be utilized to further enhance the performance of PGM-free ORR electrocatalysts.},
doi = {10.1021/acsanm.8b02235},
journal = {ACS Applied Nano Materials},
number = 3,
volume = 2,
place = {United States},
year = {2019},
month = {2}
}

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This content will become publicly available on February 1, 2020
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