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Title: Graphite Intercalation Compounds Derived by Green Chemistry as Oxygen Reduction Reaction Catalysts

Abstract

Precious group metal (PGM) catalysts such as Pt supported on carbon supports are expensive catalysts utilized for the oxygen reduction reaction (ORR) due to their unmatched catalytic activity and durability. As an alternative, PGM-free ORR electrocatalysts that offer respectable catalytic activity are being pursued. Most of the notable PGM-free catalysts are obtained either from a bottom-up approach synthesis utilizing nitrogen-rich polymers as building blocks, or from a top down approach, where nitrogen and metal moieties are incorporated to carbonaceous matrixes. The systematic understanding of the origin of catalytic activity for either case is speculative and currently employed synthesis techniques typically generate large amounts of hazardous waste such as acids, oxidizing agents, and solvents. Herein, for the first time, we investigate the catalytic activity of graphite-based materials obtained via intercalation strategies that minimally perturb the graphitic backbone. Here, our outlined approaches demonstrate initial efforts to not only elucidate the role of each element but also significantly reduce the use of hazardous chemicals, which remains a pressing challenge. Graphite intercalation compounds (GIC) were obtained using fewer steps and solvent-free processes. X-ray diffraction and Raman results confirm the successful intercalation of FeCl 3 between graphite layers. Electrochemical data shows that the ORR performancemore » of FeCl 3-intercalated GIC displays slight improvement where the onset potential reaches 0.77 V vs RHE in alkaline environments. However, expansion of the graphite and solvent-free incorporation of iron and nitrogen moieties resulted in a significant increase in ORR activity with onset potential to 0.89 V vs RHE, a maximum half-wave of 0.72 V vs RHE, and a limiting current of about 2.5 mA cm –2. We anticipate that the use of near solvent-free processes that result in a high yield of catalysts along with the fundamental insight into the origin of electrochemical activity will tremendously impact the methodologies for developing next-generation ORR catalysts.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [5];  [6]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Louisville, KY (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of Texas Rio Grande Valley, Edinburg, TX (United States)
  4. Univ. of New Mexico, Albuquerque, NM (United States)
  5. Univ. of California, Irvine, CA (United States)
  6. Univ. of Louisville, KY (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
OSTI Identifier:
1699481
Report Number(s):
LA-UR-19-30675
Journal ID: ISSN 1944-8244
Grant/Contract Number:  
89233218CNA000001; AC52-06NA25396; 1800245
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 12; Journal Issue: 38; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; graphite intercalation compounds; expanded graphite; electrocatalysts; oxygen reduction reaction; green chemistry

Citation Formats

Zhao, Jianchao, Dumont, Joseph H., Martinez, Ulises, Macossay, Javier, Artyushkova, Kateryna, Atanassov, Plamen, and Gupta, Gautam. Graphite Intercalation Compounds Derived by Green Chemistry as Oxygen Reduction Reaction Catalysts. United States: N. p., 2020. Web. doi:10.1021/acsami.0c09204.
Zhao, Jianchao, Dumont, Joseph H., Martinez, Ulises, Macossay, Javier, Artyushkova, Kateryna, Atanassov, Plamen, & Gupta, Gautam. Graphite Intercalation Compounds Derived by Green Chemistry as Oxygen Reduction Reaction Catalysts. United States. https://doi.org/10.1021/acsami.0c09204
Zhao, Jianchao, Dumont, Joseph H., Martinez, Ulises, Macossay, Javier, Artyushkova, Kateryna, Atanassov, Plamen, and Gupta, Gautam. Tue . "Graphite Intercalation Compounds Derived by Green Chemistry as Oxygen Reduction Reaction Catalysts". United States. https://doi.org/10.1021/acsami.0c09204.
@article{osti_1699481,
title = {Graphite Intercalation Compounds Derived by Green Chemistry as Oxygen Reduction Reaction Catalysts},
author = {Zhao, Jianchao and Dumont, Joseph H. and Martinez, Ulises and Macossay, Javier and Artyushkova, Kateryna and Atanassov, Plamen and Gupta, Gautam},
abstractNote = {Precious group metal (PGM) catalysts such as Pt supported on carbon supports are expensive catalysts utilized for the oxygen reduction reaction (ORR) due to their unmatched catalytic activity and durability. As an alternative, PGM-free ORR electrocatalysts that offer respectable catalytic activity are being pursued. Most of the notable PGM-free catalysts are obtained either from a bottom-up approach synthesis utilizing nitrogen-rich polymers as building blocks, or from a top down approach, where nitrogen and metal moieties are incorporated to carbonaceous matrixes. The systematic understanding of the origin of catalytic activity for either case is speculative and currently employed synthesis techniques typically generate large amounts of hazardous waste such as acids, oxidizing agents, and solvents. Herein, for the first time, we investigate the catalytic activity of graphite-based materials obtained via intercalation strategies that minimally perturb the graphitic backbone. Here, our outlined approaches demonstrate initial efforts to not only elucidate the role of each element but also significantly reduce the use of hazardous chemicals, which remains a pressing challenge. Graphite intercalation compounds (GIC) were obtained using fewer steps and solvent-free processes. X-ray diffraction and Raman results confirm the successful intercalation of FeCl3 between graphite layers. Electrochemical data shows that the ORR performance of FeCl3-intercalated GIC displays slight improvement where the onset potential reaches 0.77 V vs RHE in alkaline environments. However, expansion of the graphite and solvent-free incorporation of iron and nitrogen moieties resulted in a significant increase in ORR activity with onset potential to 0.89 V vs RHE, a maximum half-wave of 0.72 V vs RHE, and a limiting current of about 2.5 mA cm–2. We anticipate that the use of near solvent-free processes that result in a high yield of catalysts along with the fundamental insight into the origin of electrochemical activity will tremendously impact the methodologies for developing next-generation ORR catalysts.},
doi = {10.1021/acsami.0c09204},
url = {https://www.osti.gov/biblio/1699481}, journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 38,
volume = 12,
place = {United States},
year = {2020},
month = {8}
}

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