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

Xiao Xia Wang; David A. Cullen; Yung Tin Pan; Sooyeon Hwang; Maoyu Wang; Zhenxing Feng; Jingyun Wang; Mark H. Engelhard; Hanguang Zhang; Yanghua He; Yuyan Shao; Dong Su; Karren L. More; Jacob S. Spendelow; Gang Wu

doi:10.1002/adma.201706758

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

Xiao Xia Wang, David A. Cullen, Yung Tin Pan, Sooyeon Hwang, Maoyu Wang, Zhenxing Feng, Jingyun Wang, Mark H. Engelhard, Hanguang Zhang, Yanghua He, Yuyan Shao, Dong Su, Karren L. More, Jacob S. Spendelow, Gang Wu

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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). Herein, 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. 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.

Original language	English
Article number	1706758
Journal	Advanced Materials
Volume	30
Issue number	11
DOIs	https://doi.org/10.1002/adma.201706758
State	Published - Mar 15 2018

Funding

This work is financially supported from the start-up funding from the University at Buffalo, SUNY, National Science Foundation (CBET-1604392), and U.S. DOE-EERE Fuel Cell Technologies Office. Electron microscopy research was conducted at the Center for Nanophase Materials Sciences of Oak Ridge National Laboratory and the Center for Functional Nanomaterials at Brookhaven National Laboratory under Contract No. DE-SC0012704, which both are DOE Office of Science User Facilities. XAS measurements were performed at 9BM-C and 4ID-C at Advanced Photon Source of Argonne National Laboratory with support of Department of Energy under Contract No. DE-AC02-06CH11357. Z. Feng thanks the Callahan Faculty Scholar Endowment Fund from Oregon State University. X. X. Wang thanks the Shanghai Natural Science Foundation of China under Contract No. 16ZR1408600. We also thank Shiva Gupta for part of SEM analysis.

Keywords

carbon nanocomposites
electrocatalysis
oxygen reduction
proton exchange membrane fuel cells
single atomic Co

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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Wang, X. X., Cullen, D. A., Pan, Y. T., Hwang, S., Wang, M., Feng, Z., Wang, J., Engelhard, M. H., Zhang, H., He, Y., Shao, Y., Su, D., More, K. L., Spendelow, J. S., & Wu, G. (2018). Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells. Advanced Materials, 30(11), Article 1706758. https://doi.org/10.1002/adma.201706758

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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). Herein, 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. 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.",

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AU - Wang, Xiao Xia

AU - Cullen, David A.

AU - Pan, Yung Tin

AU - Hwang, Sooyeon

AU - Wang, Maoyu

AU - Feng, Zhenxing

AU - Wang, Jingyun

AU - Engelhard, Mark H.

AU - Zhang, Hanguang

AU - He, Yanghua

AU - Shao, Yuyan

AU - Su, Dong

AU - More, Karren L.

AU - Spendelow, Jacob S.

AU - Wu, Gang

PY - 2018/3/15

Y1 - 2018/3/15

N2 - 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). Herein, 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. 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.

AB - 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). Herein, 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. 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.

KW - carbon nanocomposites

KW - electrocatalysis

KW - oxygen reduction

KW - proton exchange membrane fuel cells

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

Abstract

Funding

Keywords

UN SDGs

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