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Title: Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells

Abstract

Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN 4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm -2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN 4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Comore » aggregates.« less

Authors:
 [1];  [2];  [3];  [4];  [5];  [5];  [6];  [7];  [6];  [6];  [7];  [4];  [8];  [3]; ORCiD logo [6]
  1. Univ. at Buffalo, NY (United States). Dept. of Chemical and Biological Engineering; East China Univ. of Science and Technology, Shanghai (China). School of Mechanical and Power Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  5. Oregon State Univ., Corvallis, OR (United States). School of Chemical, Biological, and Environmental Engineering
  6. Univ. at Buffalo, NY (United States). Dept. of Chemical and Biological Engineering
  7. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  8. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. at Buffalo, NY (United States); East China Univ. of Science and Technology, Shanghai (China); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); USDOE Office of Science (SC); National Science Foundation (NSF); Shanghai Natural Science Foundation of China; USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1422592
Alternate Identifier(s):
OSTI ID: 1417922; OSTI ID: 1558078
Report Number(s):
LA-UR-19-27321
Journal ID: ISSN 0935-9648; TRN: US1801631
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357; SC0012704; CBET-1604392; 16ZR1408600; 89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 11; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon nanocomposites; electrocatalysis; oxygen reduction; proton exchange membrane fuel cells; single atomic Co; Energy Sciences

Citation Formats

Wang, Xiao Xia, Cullen, David A., Pan, Yung-Tin, Hwang, Sooyeon, Wang, Maoyu, Feng, Zhenxing, Wang, Jingyun, Engelhard, Mark H., Zhang, Hanguang, He, Yanghua, Shao, Yuyan, Su, Dong, More, Karren L., Spendelow, Jacob S., and Wu, Gang. Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells. United States: N. p., 2018. Web. doi:10.1002/adma.201706758.
Wang, Xiao Xia, Cullen, David A., Pan, Yung-Tin, Hwang, Sooyeon, Wang, Maoyu, Feng, Zhenxing, Wang, Jingyun, Engelhard, Mark H., Zhang, Hanguang, He, Yanghua, Shao, Yuyan, Su, Dong, More, Karren L., Spendelow, Jacob S., & Wu, Gang. Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells. United States. doi:10.1002/adma.201706758.
Wang, Xiao Xia, Cullen, David A., Pan, Yung-Tin, Hwang, Sooyeon, Wang, Maoyu, Feng, Zhenxing, Wang, Jingyun, Engelhard, Mark H., Zhang, Hanguang, He, Yanghua, Shao, Yuyan, Su, Dong, More, Karren L., Spendelow, Jacob S., and Wu, Gang. Wed . "Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells". United States. doi:10.1002/adma.201706758. https://www.osti.gov/servlets/purl/1422592.
@article{osti_1422592,
title = {Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells},
author = {Wang, Xiao Xia and Cullen, David A. and Pan, Yung-Tin and Hwang, Sooyeon and Wang, Maoyu and Feng, Zhenxing and Wang, Jingyun and Engelhard, Mark H. and Zhang, Hanguang and He, Yanghua and Shao, Yuyan and Su, Dong and More, Karren L. and Spendelow, Jacob S. and Wu, Gang},
abstractNote = {Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). In this paper, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm-2). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. Finally, the remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.},
doi = {10.1002/adma.201706758},
journal = {Advanced Materials},
number = 11,
volume = 30,
place = {United States},
year = {2018},
month = {1}
}

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Cited by: 58 works
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Figures / Tables:

Figure 1 Figure 1: STEM images and element analysis for the best performing 20Co-NC-1100 catalysts. Aberration-corrected MAADF-STEM images (a-e) with accompanying EEL point spectra (e-f). The point spectrum in (f) was taken at the dark neighboring support area in (e) and only shows C and no any N and Co. The pointmore » spectrum (g) was taken on the bright atom in (e) and shows both Co and N, indicating that Co is coordinated with N at an atomic scale.« less

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    Works referencing / citing this record:

    Exploring the Influence of Halogen Coordination Effect of Stable Bimetallic MOFs on Oxygen Evolution Reaction
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    Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation
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