Cobalt-Based Nitride-Core Oxide-Shell Oxygen Reduction Electrocatalysts

Yang, Yao; Zeng, Rui; Xiong, Yin; DiSalvo, Francis J.; Abruña, Héctor D.

doi:10.1021/jacs.9b10809

Title: Cobalt-Based Nitride-Core Oxide-Shell Oxygen Reduction Electrocatalysts

Journal Article · Tue Nov 19 00:00:00 EST 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b10809· OSTI ID:1767665

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^[1]; Xiong, Yin ^[1]; DiSalvo, Francis J. ^[1];

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Cornell Univ., Ithaca, NY (United States)

Developing high-performance, low-cost, and conductive nonprecious electrocatalysts for the oxygen reduction reaction (ORR) has been a key challenge for advancing fuel cell technologies. Here, we report on a novel family of cobalt nitrides (Co_xN/C, x = 2, 3, 4) as ORR electrocatalysts in alkaline fuel cells. Co₄N/C exhibited the highest ORR activity among the three types of cobalt nitrides studied, with a half-wave potential (E_1/2) of 0.875 V vs RHE in 1 M KOH, rivaling that of commercial Pt/C (0.89 V). Moreover, Co₄N/C showed an 8-fold improvement in mass activity at 0.85 V, when compared to cobalt oxide, Co₃O₄/C, and a negligible degradation (ΔE_1/2 = 14 mV) after 10 000 potential cycles. The superior performance was ascribed to the formation of a conductive nitride core surrounded by a naturally formed thin oxide shell (about 2 nm). Finally, the conductive nitride core effectively mitigated the low conductivity of the metal oxide, and the thin oxide shell on the surface provided the active sites for the ORR. Strategies developed herein represent a promising approach for the design of other novel metal nitrides as electrocatalysts for fuel cells.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Alkaline-Based Energy Solutions (CABES); Cornell Univ., Ithaca, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0019445; DMR-1719875

OSTI ID:: 1767665

Journal Information:: Journal of the American Chemical Society, Vol. 141, Issue 49; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (45)

Synergistic Mn-Co catalyst outperforms Pt on high-rate oxygen reduction for alkaline polymer electrolyte fuel cells Wang, Ying; Yang, Yao; Jia, Shuangfeng Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09503-4	journal	April 2019
Ni-Doped Cobalt–Cobalt Nitride Heterostructure Arrays for High-Power Supercapacitors Liu, Ximeng; Zang, Wenjie; Guan, Cao ACS Energy Letters, Vol. 3, Issue 10 https://doi.org/10.1021/acsenergylett.8b01393	journal	September 2018
Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts Wang, Deli; Xin, Huolin L.; Hovden, Robert Nature Materials, Vol. 12, Issue 1, p. 81-87 https://doi.org/10.1038/nmat3458	journal	October 2012
Exploration of octahedrally shaped MnCo ₂ O ₄ catalyst particles for visible light driven photocatalytic water splitting reaction Shibli, S. M. A.; Arun, P. S.; Raj, Anupama V. RSC Advances, Vol. 5, Issue 25 https://doi.org/10.1039/C4RA12646G	journal	January 2015
Unification of Catalytic Water Oxidation and Oxygen Reduction Reactions: Amorphous Beat Crystalline Cobalt Iron Oxides Indra, Arindam; Menezes, Prashanth W.; Sahraie, Nastaran Ranjbar Journal of the American Chemical Society, Vol. 136, Issue 50 https://doi.org/10.1021/ja509348t	journal	December 2014
High-Loading Composition-Tolerant Co–Mn Spinel Oxides with Performance beyond 1 W/cm ² in Alkaline Polymer Electrolyte Fuel Cells Yang, Yao; Peng, Hanqing; Xiong, Yin ACS Energy Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsenergylett.9b00597	journal	May 2019
Cobalt Molybdenum Oxynitrides: Synthesis, Structural Characterization, and Catalytic Activity for the Oxygen Reduction Reaction Cao, Bingfei; Veith, Gabriel M.; Diaz, Rosa E. Angewandte Chemie International Edition, Vol. 52, Issue 41 https://doi.org/10.1002/anie.201303197	journal	August 2013
Metallic Ni ₃ N Quantum Dots as a Synergistic Promoter for NiO Nanosheet toward Efficient Oxygen Reduction Electrocatalysis Zhang, Hui; Liu, Meihuan; Cheng, Weiren The Journal of Physical Chemistry C, Vol. 123, Issue 14 https://doi.org/10.1021/acs.jpcc.9b00235	journal	March 2019
Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials Zitolo, Andrea; Goellner, Vincent; Armel, Vanessa Nature Materials, Vol. 14, Issue 9 https://doi.org/10.1038/nmat4367	journal	August 2015
Adsorption and decomposition of ammonia on W(100); XPS and UPS studies Egawa, Chikashi; Naito, Shuichi; Tamaru, Kenzi Surface Science, Vol. 131, Issue 1 https://doi.org/10.1016/0039-6028(83)90119-X	journal	August 1983
Limitations and Improvement Strategies for Early-Transition-Metal Nitrides as Competitive Catalysts toward the Oxygen Reduction Reaction Luo, Junming; Tian, Xinlong; Zeng, Jianhuang ACS Catalysis, Vol. 6, Issue 9 https://doi.org/10.1021/acscatal.6b01618	journal	August 2016
Effect of pH on the Activity of Platinum Group Metal-Free Catalysts in Oxygen Reduction Reaction Rojas-Carbonell, Santiago; Artyushkova, Kateryna; Serov, Alexey ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.7b03991	journal	March 2018
Noble-Metal-Free Iron Nitride/Nitrogen-Doped Graphene Composite for the Oxygen Reduction Reaction Varga, Tamás; Vásárhelyi, Lívia; Ballai, Gergő ACS Omega, Vol. 4, Issue 1 https://doi.org/10.1021/acsomega.8b02646	journal	January 2019
Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs Gasteiger, Hubert A.; Kocha, Shyam S.; Sompalli, Bhaskar Applied Catalysis B: Environmental, Vol. 56, Issue 1-2, p. 9-35 https://doi.org/10.1016/j.apcatb.2004.06.021	journal	March 2005
Adsorption and decomposition of ammonia on a W(110) surface: Photoemission fingerprinting and interpretation of the core level binding energies using the equivalent core approximation Grunze, M.; Brundle, C. R.; Tománek, D. Surface Science, Vol. 119, Issue 2-3 https://doi.org/10.1016/0039-6028(82)90288-6	journal	July 1982
Metallic Co ₄ N Porous Nanowire Arrays Activated by Surface Oxidation as Electrocatalysts for the Oxygen Evolution Reaction Chen, Pengzuo; Xu, Kun; Fang, Zhiwei Angewandte Chemie International Edition, Vol. 54, Issue 49 https://doi.org/10.1002/anie.201506480	journal	October 2015
Electronic Band Structure and Electrocatalytic Performance of Cu ₃ N Nanocrystals Wang, Li-Chen; Liu, Bo-Heng; Su, Chung-Yi ACS Applied Nano Materials, Vol. 1, Issue 7 https://doi.org/10.1021/acsanm.8b00787	journal	June 2018
Copper Nitride Nanocubes: Size-Controlled Synthesis and Application as Cathode Catalyst in Alkaline Fuel Cells Wu, Haibin; Chen, Wei Journal of the American Chemical Society, Vol. 133, Issue 39 https://doi.org/10.1021/ja204748u	journal	October 2011
Spinels: Controlled Preparation, Oxygen Reduction/Evolution Reaction Application, and Beyond Zhao, Qing; Yan, Zhenhua; Chen, Chengcheng Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00051	journal	July 2017
Nitrogen-Rich Manganese Oxynitrides with Enhanced Catalytic Activity in the Oxygen Reduction Reaction Miura, Akira; Rosero-Navarro, Carolina; Masubuchi, Yuji Angewandte Chemie International Edition, Vol. 55, Issue 28 https://doi.org/10.1002/anie.201601568	journal	May 2016
In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co ₄ N Hybrid for Highly Efficient Oxygen Evolution Zhu, Xiang; Jin, Tian; Tian, Chengcheng Advanced Materials, Vol. 29, Issue 47 https://doi.org/10.1002/adma.201704091	journal	October 2017
Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction Liang, Yongye; Li, Yanguang; Wang, Hailiang Nature Materials, Vol. 10, Issue 10, p. 780-786 https://doi.org/10.1038/nmat3087	journal	August 2011
The solubility and diffusion coefficient of oxygen in potassium hydroxide solutions Davis, R. E.; Horvath, G. L.; Tobias, C. W. Electrochimica Acta, Vol. 12, Issue 3, p. 287-297 https://doi.org/10.1016/0013-4686(67)80007-0	journal	March 1967
Chemical effects at metal/oxide interfaces studied by x-ray-absorption spectroscopy Regan, T. J.; Ohldag, H.; Stamm, C. Physical Review B, Vol. 64, Issue 21 https://doi.org/10.1103/PhysRevB.64.214422	journal	November 2001
2 p x-ray absorption of 3 d transition-metal compounds: An atomic multiplet description including the crystal field de Groot, F. M. F.; Fuggle, J. C.; Thole, B. T. Physical Review B, Vol. 42, Issue 9 https://doi.org/10.1103/PhysRevB.42.5459	journal	September 1990
Octahedral spinel electrocatalysts for alkaline fuel cells Yang, Yao; Xiong, Yin; Holtz, Megan E. Proceedings of the National Academy of Sciences, Vol. 116, Issue 49 https://doi.org/10.1073/pnas.1906570116	journal	November 2019
Transformation of nitrogen structures in carbonization of model compounds determined by XPS Stańczyk, Krzysztof; Dziembaj, Roman; Piwowarska, Zofia Carbon, Vol. 33, Issue 10 https://doi.org/10.1016/0008-6223(95)00084-Q	journal	January 1995
Electrocatalyst approaches and challenges for automotive fuel cells Debe, Mark K. Nature, Vol. 486, Issue 7401 https://doi.org/10.1038/nature11115	journal	June 2012
Structure and magnetization of ${Co}_{4} N$ thin film Pandey, Nidhi; Gupta, Mukul; Gupta, Rachana Journal of Magnetism and Magnetic Materials, Vol. 448 https://doi.org/10.1016/j.jmmm.2017.06.014	journal	February 2018
Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction Abroshan, Hadi; Bothra, Pallavi; Back, Seoin The Journal of Physical Chemistry C, Vol. 122, Issue 9 https://doi.org/10.1021/acs.jpcc.7b12643	journal	January 2018
Pt-Decorated Composition-Tunable Pd–Fe@Pd/C Core–Shell Nanoparticles with Enhanced Electrocatalytic Activity toward the Oxygen Reduction Reaction Xiong, Yin; Yang, Yao; DiSalvo, Francis J. Journal of the American Chemical Society, Vol. 140, Issue 23 https://doi.org/10.1021/jacs.8b03365	journal	May 2018
Energy and fuels from electrochemical interfaces Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P. Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4738	journal	December 2016
Brush-Like Cobalt Nitride Anchored Carbon Nanofiber Membrane: Current Collector-Catalyst Integrated Cathode for Long Cycle Li–O ₂ Batteries Yoon, Ki Ro; Shin, Kihyun; Park, Jiwon ACS Nano, Vol. 12, Issue 1 https://doi.org/10.1021/acsnano.7b03794	journal	December 2017
Nonprecious Metal Catalysts for Oxygen Reduction in Heterogeneous Aqueous Systems Gewirth, Andrew A.; Varnell, Jason A.; DiAscro, Angela M. Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00335	journal	December 2017
Rapid Synthesis of Cobalt Nitride Nanowires: Highly Efficient and Low-Cost Catalysts for Oxygen Evolution Zhang, Yongqi; Ouyang, Bo; Xu, Jing Angewandte Chemie International Edition, Vol. 55, Issue 30 https://doi.org/10.1002/anie.201604372	journal	June 2016
In situ electron energy loss spectroscopy study of metallic Co and Co oxides Zhao, Yuan; Feltes, Theresa E.; Regalbuto, John R. Journal of Applied Physics, Vol. 108, Issue 6 https://doi.org/10.1063/1.3482013	journal	September 2010
Revealing the atomic ordering of binary intermetallics using in situ heating techniques at multilength scales Xiong, Yin; Yang, Yao; Joress, Howie Proceedings of the National Academy of Sciences, Vol. 116, Issue 6 https://doi.org/10.1073/pnas.1815643116	journal	January 2019
Urchin-like CoP Nanocrystals as Hydrogen Evolution Reaction and Oxygen Reduction Reaction Dual-Electrocatalyst with Superior Stability Yang, Hongchao; Zhang, Yejun; Hu, Feng Nano Letters, Vol. 15, Issue 11 https://doi.org/10.1021/acs.nanolett.5b03446	journal	October 2015
Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki Nature Chemistry, Vol. 3, Issue 7, p. 546-550 https://doi.org/10.1038/nchem.1069	journal	June 2011
Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst Chung, Hoon T.; Cullen, David A.; Higgins, Drew Science, Vol. 357, Issue 6350 https://doi.org/10.1126/science.aan2255	journal	August 2017
Metal–Organic-Framework-Derived Co–Fe Bimetallic Oxygen Reduction Electrocatalysts for Alkaline Fuel Cells Xiong, Yin; Yang, Yao; DiSalvo, Francis J. Journal of the American Chemical Society, Vol. 141, Issue 27 https://doi.org/10.1021/jacs.9b03561	journal	June 2019
In Situ X-ray Absorption Spectroscopy of a Synergistic Co–Mn Oxide Catalyst for the Oxygen Reduction Reaction Yang, Yao; Wang, Ying; Xiong, Yin Journal of the American Chemical Society, Vol. 141, Issue 4 https://doi.org/10.1021/jacs.8b12243	journal	December 2018
Preparation of Co-N films by rf-sputtering Oda, Kiichi; Yoshio, Tetsuo; Oda, Kohei Journal of Materials Science, Vol. 22, Issue 8 https://doi.org/10.1007/BF01086464	journal	August 1987
A Strategy for Increasing the Efficiency of the Oxygen Reduction Reaction in Mn-Doped Cobalt Ferrites Xiong, Yin; Yang, Yao; Feng, Xinran Journal of the American Chemical Society, Vol. 141, Issue 10 https://doi.org/10.1021/jacs.8b13296	journal	February 2019
In Situ Coupling of Strung Co ₄ N and Intertwined N–C Fibers toward Free-Standing Bifunctional Cathode for Robust, Efficient, and Flexible Zn–Air Batteries Meng, Fanlu; Zhong, Haixia; Bao, Di Journal of the American Chemical Society, Vol. 138, Issue 32 https://doi.org/10.1021/jacs.6b05046	journal	August 2016

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Title: Cobalt-Based Nitride-Core Oxide-Shell Oxygen Reduction Electrocatalysts

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