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Title: Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells

Abstract

The development of catalysts free of platinum-group metals and with both a high activity and durability for the oxygen reduction reaction in proton exchange membrane fuel cells is a grand challenge. In this paper, we report an atomically dispersed Co and N co-doped carbon (Co–N–C) catalyst with a high catalytic oxygen reduction reaction activity comparable to that of a similarly synthesized Fe–N–C catalyst but with a four-time enhanced durability. The Co–N–C catalyst achieved a current density of 0.022 A cm-2 at 0.9 ViR-free (internal resistance-compensated voltage) and peak power density of 0.64 W cm-2 in 1.0 bar H2/O2 fuel cells, higher than that of non-iron platinum-group-metal-free catalysts reported in the literature. Importantly, we identified two main degradation mechanisms for metal (M)–N–C catalysts: catalyst oxidation by radicals and active-site demetallation. The enhanced durability of Co–N–C relative to Fe–N–C is attributed to the lower activity of Co ions for Fenton reactions that produce radicals from the main oxygen reduction reaction by-product, H2O2, and the significantly enhanced resistance to demetallation of Co–N–C.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [5];  [6]; ORCiD logo [6]; ORCiD logo [7];  [8]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [1];  [6]; ORCiD logo [7];  [3]; ORCiD logo [4] more »; ORCiD logo [2]; ORCiD logo [1] « less
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Washington Univ., St. Louis, MO (United States)
  3. Univ. of Pittsburgh, PA (United States)
  4. Univ. at Buffalo, NY (United States)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. Argonne National Lab. (ANL), Argonne, IL (United States)
  7. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  8. Northern Illinois Univ., DeKalb, IL (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF)
OSTI Identifier:
1737646
Alternate Identifier(s):
OSTI ID: 1819652
Grant/Contract Number:  
AC05-00OR22725; AC05-76RLO1830; AC02-06CH11357; ACI-1053575
Resource Type:
Accepted Manuscript
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 3; Journal Issue: 12; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Xie, Xiaohong, He, Cheng, Li, Boyang, He, Yanghua, Cullen, David A., Wegener, Evan C., Kropf, A. Jeremy, Martinez, Ulises, Cheng, Yingwen, Engelhard, Mark H., Bowden, Mark E., Song, Miao, Lemmon, Teresa, Li, Xiaohong S., Nie, Zimin, Liu, Jian, Myers, Deborah J., Zelenay, Piotr, Wang, Guofeng, Wu, Gang, Ramani, Vijay, and Shao, Yuyan. Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells. United States: N. p., 2020. Web. https://doi.org/10.1038/s41929-020-00546-1.
Xie, Xiaohong, He, Cheng, Li, Boyang, He, Yanghua, Cullen, David A., Wegener, Evan C., Kropf, A. Jeremy, Martinez, Ulises, Cheng, Yingwen, Engelhard, Mark H., Bowden, Mark E., Song, Miao, Lemmon, Teresa, Li, Xiaohong S., Nie, Zimin, Liu, Jian, Myers, Deborah J., Zelenay, Piotr, Wang, Guofeng, Wu, Gang, Ramani, Vijay, & Shao, Yuyan. Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells. United States. https://doi.org/10.1038/s41929-020-00546-1
Xie, Xiaohong, He, Cheng, Li, Boyang, He, Yanghua, Cullen, David A., Wegener, Evan C., Kropf, A. Jeremy, Martinez, Ulises, Cheng, Yingwen, Engelhard, Mark H., Bowden, Mark E., Song, Miao, Lemmon, Teresa, Li, Xiaohong S., Nie, Zimin, Liu, Jian, Myers, Deborah J., Zelenay, Piotr, Wang, Guofeng, Wu, Gang, Ramani, Vijay, and Shao, Yuyan. Mon . "Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells". United States. https://doi.org/10.1038/s41929-020-00546-1. https://www.osti.gov/servlets/purl/1737646.
@article{osti_1737646,
title = {Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells},
author = {Xie, Xiaohong and He, Cheng and Li, Boyang and He, Yanghua and Cullen, David A. and Wegener, Evan C. and Kropf, A. Jeremy and Martinez, Ulises and Cheng, Yingwen and Engelhard, Mark H. and Bowden, Mark E. and Song, Miao and Lemmon, Teresa and Li, Xiaohong S. and Nie, Zimin and Liu, Jian and Myers, Deborah J. and Zelenay, Piotr and Wang, Guofeng and Wu, Gang and Ramani, Vijay and Shao, Yuyan},
abstractNote = {The development of catalysts free of platinum-group metals and with both a high activity and durability for the oxygen reduction reaction in proton exchange membrane fuel cells is a grand challenge. In this paper, we report an atomically dispersed Co and N co-doped carbon (Co–N–C) catalyst with a high catalytic oxygen reduction reaction activity comparable to that of a similarly synthesized Fe–N–C catalyst but with a four-time enhanced durability. The Co–N–C catalyst achieved a current density of 0.022 A cm-2 at 0.9 ViR-free (internal resistance-compensated voltage) and peak power density of 0.64 W cm-2 in 1.0 bar H2/O2 fuel cells, higher than that of non-iron platinum-group-metal-free catalysts reported in the literature. Importantly, we identified two main degradation mechanisms for metal (M)–N–C catalysts: catalyst oxidation by radicals and active-site demetallation. The enhanced durability of Co–N–C relative to Fe–N–C is attributed to the lower activity of Co ions for Fenton reactions that produce radicals from the main oxygen reduction reaction by-product, H2O2, and the significantly enhanced resistance to demetallation of Co–N–C.},
doi = {10.1038/s41929-020-00546-1},
journal = {Nature Catalysis},
number = 12,
volume = 3,
place = {United States},
year = {2020},
month = {11}
}

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