Nitrogen-Doped Graphene Oxide Electrocatalysts for the Oxygen Reduction Reaction

doi:https://doi.org/10.1021/acsanm.8b02235

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 »« less

Authors:

^[1];

^[2];

^[3]; Purdy, Geraldine M. ^[2]; Dattelbaum, Andrew M. ^[2];

^[2];

^[3]; Gupta, Gautam ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of New Mexico, Albuquerque, NM (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Univ. of New Mexico, Albuquerque, NM (United States)

Publication Date:: 2019-02-01

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:: Journal Article: 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.

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                    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.  https://doi.org/10.1021/acsanm.8b02235

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                    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.  https://doi.org/10.1021/acsanm.8b02235.  https://www.osti.gov/servlets/purl/1495149.

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@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},

  url          = {https://www.osti.gov/biblio/1495149},
  journal      = {ACS Applied Nano Materials},

  issn         = {2574-0970},

  number       = 3,

  volume       = 2,

  place        = {United States},

  year         = {2019},

  month        = {2}

}

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Works referencing / citing this record:

An efficient metal-free catalyst derived from waste lotus seedpod for oxygen reduction reaction
journal, January 2020

Zheng, Bo; Wang, Jiaxin; Pan, Zhaorui
Journal of Porous Materials, Vol. 27, Issue 3
https://doi.org/10.1007/s10934-019-00846-3

Simple Self-assembly Synthesis for Cost-Effective Alkaline Fuel Cell Bi-functional Electrocatalyst Synthesized from Polyethylene Terephthalate Waste Bottles
journal, October 2019

Elessawy, Noha A.; Elnouby, Mohamed; Gouda, M.
Journal of Electronic Materials, Vol. 49, Issue 2
https://doi.org/10.1007/s11664-019-07684-8

The magnetic graphene oxide/NHC catalyzed aerobic direct amidation and cross-dehydrogenative coupling of aldehydes
journal, January 2019

Sepahvand, Heshmatollah; Ghasemi, Elnaz; Sharbati, Mohammad
New Journal of Chemistry, Vol. 43, Issue 42
https://doi.org/10.1039/c9nj04343h

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

Abstract

Citation Formats

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Simple Self-assembly Synthesis for Cost-Effective Alkaline Fuel Cell Bi-functional Electrocatalyst Synthesized from Polyethylene Terephthalate Waste Bottles journal, October 2019

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journal, October 2019

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journal, January 2019