Improved Oxygen Reduction Reaction Activity of Nanostructured CoS2 through Electrochemical Tuning

Zhao, Wei-Wei; Bothra, Pallavi; Lu, Zhiyi; Li, Yanbin; Mei, Li-Ping; Liu, Kai; Zhao, Zhenghang; Chen, Guangxu; Back, Seoin; Siahrostami, Samira; Kulkarni, Ambarish; Nørskov, Jens K.; Bajdich, Michal; Cui, Yi

doi:10.1021/acsaem.9b01527

Improved Oxygen Reduction Reaction Activity of Nanostructured CoS₂ through Electrochemical Tuning

Journal Article · Thu Oct 24 00:00:00 EDT 2019 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.9b01527· OSTI ID:1605394

^[1]; Bothra, Pallavi ^[2]; Lu, Zhiyi ^[3]; ^[4]; Mei, Li-Ping ^[4]; ^[5]; Zhao, Zhenghang ^[2]; Chen, Guangxu ^[5]; Back, Seoin ^[2]; ^[2]; Kulkarni, Ambarish ^[2]; Nørskov, Jens K. ^[6]; ^[7]; ^[3]

Nanjing Univ. (China); Stanford Univ., CA (United States)
Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Chemical Engineering
Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
Nanjing Univ. (China)
Stanford Univ., CA (United States)
Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Chemical Engineering; Technical Univ. of Denmark, Lyngby (Denmark)
SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis

Searching for efficient Pt-free oxygen reduction reaction (ORR) electrocatalysts has been actively pursued among the current electrocatalyst research community. The family of transition-metal chalcogenides, especially cobalt disulfide (CoS₂), has been reported as competitive ORR catalysts. In this work, we perform a detailed analysis of the intrinsic activity in terms of onset potentials and selectivity toward hydrogen peroxide of CoS₂ in both acid and alkaline medium. Our detailed characterizations of this system via X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and calculated bulk and surface thermodynamics and ORR mechanism reveal pH-dependent electrochemical evolution of the CoS₂ surfaces. Using XPS results before and after ORR in combination with density functional theory (DFT) calculations for individual surfaces reveals sulfur to oxygen substitution, and partial dissolution occurs in acidic media, while thin cobalt oxide films supported by CoS₂ are formed in alkaline media. The comprehensive DFT calculations of the ORR activities on these systems reveal that sulfur is an unlikely ORR active site, while undercoordinated Co metal site in the CoS₂ is less active than very active undercoordinated Co metal site in the Co oxide film. Using these guiding principles, we then demonstrate that electrochemical lithium (Li) tuning of CoS₂ in organic electrolyte increases its ORR performance in both acid and alkaline medium. Detailed characterizations demonstrate that the grain size of CoS₂ particle is considerably reduced and has a much richer surface oxygen content after electrochemical Li tuning (LiET-CoS₂) as the direct consequence of the Li galvanostatic cycling. The general efficacy of this method toward transition-metal chalcogenides (T-M-X) is further demonstrated by enhanced ORR activities of CoS and Ni₃S₂ in alkaline and neutral medium, respectively. This work opens up an opportunity for probing more advanced T-M-X-based catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); Natural Science Foundation of Jiangsu Province; Toyota Research Institute; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1605394

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 12 Vol. 2; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (36)

Thermochemical Data of Pure Substances Barin, Ihsan https://doi.org/10.1002/9783527619825	book	October 1995
Selective Electrochemical H ₂ O ₂ Production through Two-Electron Oxygen Electrochemistry Jiang, Yuanyuan; Ni, Pengjuan; Chen, Chuanxia Advanced Energy Materials, Vol. 8, Issue 31 https://doi.org/10.1002/aenm.201801909	journal	September 2018
Co1−xS-Graphene Hybrid: A High-Performance Metal Chalcogenide Electrocatalyst for Oxygen Reduction Wang, Hailiang; Liang, Yongye; Li, Yanguang Angewandte Chemie International Edition, Vol. 50, Issue 46 https://doi.org/10.1002/anie.201104004	journal	September 2011
Trends in Oxygen Electrocatalysis of 3 d ‐Layered (Oxy)(Hydro)Oxides Zhao, Zhenghang; Schlexer Lamoureux, Philomena; Kulkarni, Ambarish ChemCatChem, Vol. 11, Issue 15 https://doi.org/10.1002/cctc.201900846	journal	June 2019
Interfacial properties of oxides with technological impact in electrochemistry Ardizzone, S.; Trasatti, S. Advances in Colloid and Interface Science, Vol. 64 https://doi.org/10.1016/0001-8686(95)00286-3	journal	February 1996
Electrocatalytic oxygen reduction with thiospinels and other sulphides of transition metals Behret, H.; Binder, H.; Sandstede, G. Electrochimica Acta, Vol. 20, Issue 2 https://doi.org/10.1016/0013-4686(75)90047-X	journal	February 1975
Activation of a Ni electrocatalyst through spontaneous transformation of nickel sulfide to nickel hydroxide in an oxygen evolution reaction Lee, Minoh; Oh, Hyung-Suk; Cho, Min Kyung Applied Catalysis B: Environmental, Vol. 233 https://doi.org/10.1016/j.apcatb.2018.03.083	journal	October 2018
Potential–pH diagram for sulfur and hydroxyl adsorbed on silver in water containing sulfides Protopopoff, Elie; Marcus, Philippe Electrochimica Acta, Vol. 63 https://doi.org/10.1016/j.electacta.2011.12.030	journal	February 2012
Surface Restructuring of Nickel Sulfide Generates Optimally Coordinated Active Sites for Oxygen Reduction Catalysis Yan, Bing; Krishnamurthy, Dilip; Hendon, Christopher H. Joule, Vol. 1, Issue 3 https://doi.org/10.1016/j.joule.2017.08.020	journal	November 2017
A study of novel anode material CoS2 for lithium ion battery Yan, J. M.; Huang, H. Z.; Zhang, J. Journal of Power Sources, Vol. 146, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2005.03.144	journal	August 2005
Recent Advances in Electrocatalysts for Oxygen Reduction Reaction Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol Chemical Reviews, Vol. 116, Issue 6 https://doi.org/10.1021/acs.chemrev.5b00462	journal	February 2016
Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction Kulkarni, Ambarish; Siahrostami, Samira; Patel, Anjli Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00488	journal	December 2017
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
Monodisperse Palladium Sulfide as Efficient Electrocatalyst for Oxygen Reduction Reaction Du, Cheng; Li, Peng; Yang, Fulin ACS Applied Materials & Interfaces, Vol. 10, Issue 1 https://doi.org/10.1021/acsami.7b16359	journal	December 2017
Cobalt Sulfide Nanoparticles Grown on Nitrogen and Sulfur Codoped Graphene Oxide: An Efficient Electrocatalyst for Oxygen Reduction and Evolution Reactions Ganesan, Pandian; Prabu, Moni; Sanetuntikul, Jakkid ACS Catalysis, Vol. 5, Issue 6 https://doi.org/10.1021/acscatal.5b00154	journal	May 2015
In Situ Transformation of Hydrogen-Evolving CoP Nanoparticles: Toward Efficient Oxygen Evolution Catalysts Bearing Dispersed Morphologies with Co-oxo/hydroxo Molecular Units Ryu, Jaeyune; Jung, Namgee; Jang, Jong Hyun ACS Catalysis, Vol. 5, Issue 7 https://doi.org/10.1021/acscatal.5b00349	journal	June 2015
Electrocatalytic Production of H ₂ O ₂ by Selective Oxygen Reduction Using Earth-Abundant Cobalt Pyrite (CoS ₂ ) Sheng, Hongyuan; Hermes, Eric D.; Yang, Xiaohua ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b02546	journal	August 2019
Platinum-Based Oxygen Reduction Electrocatalysts Wu, Jianbo; Yang, Hong Accounts of Chemical Research, Vol. 46, Issue 8 https://doi.org/10.1021/ar300359w	journal	April 2013
Nanostructured Nonprecious Metal Catalysts for Oxygen Reduction Reaction Wu, Gang; Zelenay, Piotr Accounts of Chemical Research, Vol. 46, Issue 8 https://doi.org/10.1021/ar400011z	journal	April 2013
Metal-Free Catalysts for Oxygen Reduction Reaction Dai, Liming; Xue, Yuhua; Qu, Liangti Chemical Reviews, Vol. 115, Issue 11 https://doi.org/10.1021/cr5003563	journal	May 2015
Universality in Oxygen Reduction Electrocatalysis on Metal Surfaces Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan ACS Catalysis, Vol. 2, Issue 8 https://doi.org/10.1021/cs300227s	journal	July 2012
Identifying the Active Surfaces of Electrochemically Tuned LiCoO ₂ for Oxygen Evolution Reaction Lu, Zhiyi; Chen, Guangxu; Li, Yanbin Journal of the American Chemical Society, Vol. 139, Issue 17 https://doi.org/10.1021/jacs.7b02622	journal	April 2017
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction Lu, Zhiyi; Wang, Haotian; Kong, Desheng Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5345	journal	July 2014
Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting Wang, Haotian; Lee, Hyun-Wook; Deng, Yong Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8261	journal	June 2015
Catalysis-Hub.org, an open electronic structure database for surface reactions Winther, Kirsten T.; Hoffmann, Max J.; Boes, Jacob R. Scientific Data, Vol. 6, Issue 1 https://doi.org/10.1038/s41597-019-0081-y	journal	May 2019
A universal principle for a rational design of single-atom electrocatalysts Xu, Haoxiang; Cheng, Daojian; Cao, Dapeng Nature Catalysis, Vol. 1, Issue 5 https://doi.org/10.1038/s41929-018-0063-z	journal	April 2018
Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction Nie, Yao; Li, Li; Wei, Zidong Chemical Society Reviews, Vol. 44, Issue 8 https://doi.org/10.1039/C4CS00484A	journal	January 2015
An amorphous CoSe film behaves as an active and stable full water-splitting electrocatalyst under strongly alkaline conditions Liu, Tingting; Liu, Qian; Asiri, Abdullah M. Chemical Communications, Vol. 51, Issue 93 https://doi.org/10.1039/C5CC06892D	journal	January 2015
Electrochemical tuning of olivine-type lithium transition-metal phosphates as efficient water oxidation catalysts Liu, Yayuan; Wang, Haotian; Lin, Dingchang Energy & Environmental Science, Vol. 8, Issue 6 https://doi.org/10.1039/C5EE01290B	journal	January 2015
Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction Wang, H.; Lu, Z.; Xu, S. Proceedings of the National Academy of Sciences, Vol. 110, Issue 49 https://doi.org/10.1073/pnas.1316792110	journal	November 2013
Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction Yang, Liu; Cheng, Daojian; Xu, Haoxiang Proceedings of the National Academy of Sciences, Vol. 115, Issue 26 https://doi.org/10.1073/pnas.1800771115	journal	June 2018
Charge densities in CoS2 and NiS2 (pyrite structure) Nowack, E.; Schwarzenbach, D.; Hahn, Th. Acta Crystallographica Section B Structural Science, Vol. 47, Issue 5 https://doi.org/10.1107/S0108768191004871	journal	October 1991
High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt Wu, G.; More, K. L.; Johnston, C. M. Science, Vol. 332, Issue 6028, p. 443-447 https://doi.org/10.1126/science.1200832	journal	April 2011
Direct and continuous strain control of catalysts with tunable battery electrode materials Wang, Haotian; Xu, Shicheng; Tsai, Charlie Science, Vol. 354, Issue 6315 https://doi.org/10.1126/science.aaf7680	journal	November 2016
Rationalization of the Low-Potential Reactivity of 3d-Metal-Based Inorganic Compounds toward Li Poizot, P.; Laruelle, S.; Grugeon, S. Journal of The Electrochemical Society, Vol. 149, Issue 9 https://doi.org/10.1149/1.1497981	journal	January 2002

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CoS2
Pourbaix diagram
electrochemical lithium tuning
grain boundaries
oxygen reduction reaction
theoretical overpotential
transition metal chalcogenides