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

Xiaohong Xie; Cheng He; Boyang Li; Yanghua He; David A. Cullen; Evan C. Wegener; A. Jeremy Kropf; Ulises Martinez; Yingwen Cheng; Mark H. Engelhard; Mark E. Bowden; Miao Song; Teresa Lemmon; Xiaohong S. Li; Zimin Nie; Jian Liu; Deborah J. Myers; Piotr Zelenay; Guofeng Wang; Gang Wu; Vijay Ramani; Yuyan Shao

doi:10.1038/s41929-020-00546-1

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

Xiaohong Xie, Cheng He, Boyang Li, Yanghua He, David A. Cullen, Evan C. Wegener, A. Jeremy Kropf, Ulises Martinez, Yingwen Cheng, Mark H. Engelhard, Mark E. Bowden, Miao Song, Teresa Lemmon, Xiaohong S. Li, Zimin Nie, Jian Liu, Deborah J. Myers, Piotr Zelenay, Guofeng Wang, Gang WuVijay Ramani, Yuyan Shao

Materials MicroAnalysis

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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. Here 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 V_iR-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. [Figure not available: see fulltext.]

Original language	English
Pages (from-to)	1044-1054
Number of pages	11
Journal	Nature Catalysis
Volume	3
Issue number	12
DOIs	https://doi.org/10.1038/s41929-020-00546-1
State	Published - Dec 2020

Funding

The authors acknowledge support from the US Department of Energy, Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office (DOE-EERE-HFTO) through the Electrocatalysis consortium (ElectroCat) and the DOE programme managers, D. Papageorgopoulos, S. Thompson, D. Peterson and G. Kleen. The XPS measurement was performed using EMSL(grid.436923.9), a DOE Office of Science user facility sponsored by the Biological and Environmental Research programme. PNNL is operated by Battelle for the US DOE under contract DE-AC05-76RLO1830. X-ray spectroscopy experiments were performed at MRCAT at the Advanced Photon Source (APS), a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. The operation of MRCAT is supported both by DOE and the MRCAT member institutions. Argonne National Laboratory is operated for the US DOE by the University of Chicago Argonne LLC under contract no. DE-AC02-06CH11357. Electron microscopy was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. The DFT calculations were performed on the computers of the University of Pittsburgh Center for Research Computing as well as the Extreme Science and Engineering Discovery Environment (XSEDE), which is funded by National Science Foundation grant no. ACI-1053575.

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Xie, X., He, C., Li, B., He, Y., Cullen, D. A., Wegener, E. C., Kropf, A. J., Martinez, U., Cheng, Y., Engelhard, M. H., Bowden, M. E., Song, M., Lemmon, T., Li, X. S., Nie, Z., Liu, J., Myers, D. J., Zelenay, P., Wang, G., ... Shao, Y. (2020). Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells. Nature Catalysis, 3(12), 1044-1054. https://doi.org/10.1038/s41929-020-00546-1

@article{a8ab6fe407554f5e83f2d141d337845b,

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. Here 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. [Figure not available: see fulltext.]",

author = "Xiaohong Xie and Cheng He and Boyang Li and Yanghua He and Cullen, {David A.} and Wegener, {Evan C.} and Kropf, {A. Jeremy} and Ulises Martinez and Yingwen Cheng and Engelhard, {Mark H.} and Bowden, {Mark E.} and Miao Song and Teresa Lemmon and Li, {Xiaohong S.} and Zimin Nie and Jian Liu and Myers, {Deborah J.} and Piotr Zelenay and Guofeng Wang and Gang Wu and Vijay Ramani and Yuyan Shao",

note = "Publisher Copyright: {\textcopyright} 2020, This is a U.S. government work and not under copyright protection in the U.S.; foreign copyright protection may apply.",

year = "2020",

month = dec,

doi = "10.1038/s41929-020-00546-1",

language = "English",

volume = "3",

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journal = "Nature Catalysis",

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Xie, X, He, C, Li, B, He, Y, Cullen, DA, Wegener, EC, Kropf, AJ, Martinez, U, Cheng, Y, Engelhard, MH, Bowden, ME, Song, M, Lemmon, T, Li, XS, Nie, Z, Liu, J, Myers, DJ, Zelenay, P, Wang, G, Wu, G, Ramani, V & Shao, Y 2020, 'Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells', Nature Catalysis, vol. 3, no. 12, pp. 1044-1054. https://doi.org/10.1038/s41929-020-00546-1

TY - JOUR

T1 - Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells

AU - Xie, Xiaohong

AU - He, Cheng

AU - Li, Boyang

AU - He, Yanghua

AU - Cullen, David A.

AU - Wegener, Evan C.

AU - Kropf, A. Jeremy

AU - Martinez, Ulises

AU - Cheng, Yingwen

AU - Engelhard, Mark H.

AU - Bowden, Mark E.

AU - Song, Miao

AU - Lemmon, Teresa

AU - Li, Xiaohong S.

AU - Nie, Zimin

AU - Liu, Jian

AU - Myers, Deborah J.

AU - Zelenay, Piotr

AU - Wang, Guofeng

AU - Wu, Gang

AU - Ramani, Vijay

AU - Shao, Yuyan

PY - 2020/12

Y1 - 2020/12

N2 - 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. Here 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. [Figure not available: see fulltext.]

AB - 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. Here 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. [Figure not available: see fulltext.]

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U2 - 10.1038/s41929-020-00546-1

DO - 10.1038/s41929-020-00546-1

M3 - Article

AN - SCOPUS:85096904155

SN - 2520-1158

VL - 3

SP - 1044

EP - 1054

JO - Nature Catalysis

JF - Nature Catalysis

IS - 12

ER -

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

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