Enhancing Catalytic Activity of MoS2 Basal Plane S-Vacancy by Co Cluster Addition

Park, Sangwook; Park, Joonsuk; Abroshan, Hadi; Zhang, Liang; Kim, Jung Kyu; Zhang, Jiaming; Guo, Jinghua; Siahrostami, Samira; Zheng, Xiaolin

doi:10.1021/acsenergylett.8b01567

Enhancing Catalytic Activity of MoS2 Basal Plane S-Vacancy by Co Cluster Addition

Journal Article · Mon Oct 08 00:00:00 EDT 2018 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.8b01567· OSTI ID:1656475

^[1]; Park, Joonsuk ^[1]; ^[2]; ^[3]; ^[4]; Zhang, Jiaming ^[5]; ^[3]; ^[2]; ^[1]

Stanford Univ., CA (United States)
Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Sungkyunkwan Univ., Suwon (South Korea)
Hewlett-Packard Labs., Palo Alto, CA (United States)

The basal plane of molybdenum disulfide (MoS₂) was recently activated for hydrogen evolution reaction (HER) by creating sulfur (S) vacancies (MoS_2-x). However, the HER activity of those S-vacancies depends on the concentration of S-vacancies, imposing a dilemma for either improving activity per site or increasing overall active site density. In this work, we use density functional theory (DFT) calculations and experiments to show that the HER activities of MoS2-x are greatly enhanced by adding cobalt (Co) clusters on the basal plane. Furthermore, our DFT results show that the highest HER activity is achieved when the Co clusters are anchored on the S-vacancies with the interface of Co-Mo as the preferred active site. Our experiments confirm that the addition of Co enhances the activity per unit active site and increases the electrochemical active surface area. These results demonstrate the basal plane activity of MoS_2-x can be enhanced by decorating S-vacancies with transition-metal clusters.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1656475

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 11 Vol. 3; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (33)

Dual-Native Vacancy Activated Basal Plane and Conductivity of MoSe ₂ with High-Efficiency Hydrogen Evolution Reaction Gao, Daqiang; Xia, Baorui; Wang, Yanyan Small, Vol. 14, Issue 14 https://doi.org/10.1002/smll.201704150	journal	February 2018
Insights into water–gas shift reaction mechanisms over MoS2 and Co-MoS2 catalysts: a density functional study Zhang, Chunyun; Liu, Bonan; Zhao, Liang Reaction Kinetics, Mechanisms and Catalysis, Vol. 120, Issue 2 https://doi.org/10.1007/s11144-017-1146-6	journal	February 2017
Transition-metal doped edge sites in vertically aligned MoS2 catalysts for enhanced hydrogen evolution Wang, Haotian; Tsai, Charlie; Kong, Desheng Nano Research, Vol. 8, Issue 2 https://doi.org/10.1007/s12274-014-0677-7	journal	January 2015
Functional MoS2 by the Co/Ni doping as the catalyst for oxygen reduction reaction Xiao, B. B.; Zhang, P.; Han, L. P. Applied Surface Science, Vol. 354 https://doi.org/10.1016/j.apsusc.2014.12.134	journal	November 2015
Efficient Electrocatalytic and Photoelectrochemical Hydrogen Generation Using MoS 2 and Related Compounds Ding, Qi; Song, Bo; Xu, Ping Chem, Vol. 1, Issue 5 https://doi.org/10.1016/j.chempr.2016.10.007	journal	November 2016
Theoretical insights into the hydrogen evolution activity of layered transition metal dichalcogenides Tsai, Charlie; Chan, Karen; Nørskov, Jens K. Surface Science, Vol. 640 https://doi.org/10.1016/j.susc.2015.01.019	journal	October 2015
Defects Engineered Monolayer MoS ₂ for Improved Hydrogen Evolution Reaction Ye, Gonglan; Gong, Yongji; Lin, Junhao Nano Letters, Vol. 16, Issue 2 https://doi.org/10.1021/acs.nanolett.5b04331	journal	January 2016
General Thermal Texturization Process of MoS ₂ for Efficient Electrocatalytic Hydrogen Evolution Reaction Kiriya, Daisuke; Lobaccaro, Peter; Nyein, Hnin Yin Yin Nano Letters, Vol. 16, Issue 7 https://doi.org/10.1021/acs.nanolett.6b00569	journal	June 2016
Enabling Colloidal Synthesis of Edge-Oriented MoS ₂ with Expanded Interlayer Spacing for Enhanced HER Catalysis Sun, Yugang; Alimohammadi, Farbod; Zhang, Dongtang Nano Letters, Vol. 17, Issue 3 https://doi.org/10.1021/acs.nanolett.6b05346	journal	February 2017
Co-Doped MoS ₂ Nanosheets with the Dominant CoMoS Phase Coated on Carbon as an Excellent Electrocatalyst for Hydrogen Evolution Dai, Xiaoping; Du, Kangli; Li, Zhanzhao ACS Applied Materials & Interfaces, Vol. 7, Issue 49 https://doi.org/10.1021/acsami.5b08420	journal	December 2015
Ar ²⁺ Beam Irradiation-Induced Multivancancies in MoSe ₂ Nanosheet for Enhanced Electrochemical Hydrogen Evolution Xia, Baorui; Wang, Tongtong; Jiang, Xingdong ACS Energy Letters, Vol. 3, Issue 9 https://doi.org/10.1021/acsenergylett.8b01209	journal	August 2018
Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide Nanomaterials Benck, Jesse D.; Hellstern, Thomas R.; Kibsgaard, Jakob ACS Catalysis, Vol. 4, Issue 11 https://doi.org/10.1021/cs500923c	journal	October 2014
Biomimetic Hydrogen Evolution: MoS ₂ Nanoparticles as Catalyst for Hydrogen Evolution Hinnemann, Berit; Moses, Poul Georg; Bonde, Jacob Journal of the American Chemical Society, Vol. 127, Issue 15 https://doi.org/10.1021/ja0504690	journal	April 2005
Kinetic Study of Hydrogen Evolution Reaction over Strained MoS ₂ with Sulfur Vacancies Using Scanning Electrochemical Microscopy Li, Hong; Du, Minshu; Mleczko, Michal J. Journal of the American Chemical Society, Vol. 138, Issue 15 https://doi.org/10.1021/jacs.6b01377	journal	April 2016
Contributions of Phase, Sulfur Vacancies, and Edges to the Hydrogen Evolution Reaction Catalytic Activity of Porous Molybdenum Disulfide Nanosheets Yin, Ying; Han, Jiecai; Zhang, Yumin Journal of the American Chemical Society, Vol. 138, Issue 25 https://doi.org/10.1021/jacs.6b03714	journal	June 2016
Mechanisms and Energies of Water Gas Shift Reaction on Fe-, Co-, and Ni-Promoted MoS ₂ Catalysts Chen, Yan-Yan; Dong, Mei; Wang, Jianguo The Journal of Physical Chemistry C, Vol. 116, Issue 48 https://doi.org/10.1021/jp308383r	journal	November 2012
Growth of Large-Area and Highly Crystalline MoS₂ Thin Layers on Insulating Substrates Liu, Keng-Ku; Zhang, Wenjing; Lee, Yi-Hsien Nano Letters, Vol. 12, Issue 3, p. 1538-1544 https://doi.org/10.1021/nl2043612	journal	February 2012
Synthesis of MoS₂ and MoSe₂ Films with Vertically Aligned Layers Kong, Desheng; Wang, Haotian; Cha, Judy J. Nano Letters, Vol. 13, Issue 3, p. 1341-1347 https://doi.org/10.1021/nl400258t	journal	February 2013
Alternative energy technologies Dresselhaus, M. S.; Thomas, I. L. Nature, Vol. 414, Issue 6861 https://doi.org/10.1038/35104599	journal	November 2001
MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction Liu, Guoliang; Robertson, Alex W.; Li, Molly Meng-Jung Nature Chemistry, Vol. 9, Issue 8 https://doi.org/10.1038/nchem.2740	journal	March 2017
Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution Tsai, Charlie; Li, Hong; Park, Sangwook Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15113	journal	April 2017
Engineering the surface structure of MoS₂ to preferentially expose active edge sites for electrocatalysis Kibsgaard, Jakob; Chen, Zhebo; Reinecke, Benjamin N. Nature Materials, Vol. 11, Issue 11, p. 963-969 https://doi.org/10.1038/nmat3439	journal	October 2012
Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies Li, Hong; Tsai, Charlie; Koh, Ai Leen Nature Materials, Vol. 15, Issue 1 https://doi.org/10.1038/nmat4465	journal	November 2015
Design of active and stable Co–Mo–Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction Staszak-Jirkovský, Jakub; Malliakas, Christos D.; Lopes, Pietro P. Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4481	journal	November 2015
Mechanochemically induced transformation of CoO(OH) into Co ₃ O ₄ nanoparticles and their highly reversible Li storage characteristics Park, Jae-Wan; Park, Cheol-Min RSC Advances, Vol. 7, Issue 17 https://doi.org/10.1039/C6RA26099C	journal	January 2017
Detection of defect populations in superhard semiconductor boron subphosphide B ₁₂ P ₂ through X-ray absorption spectroscopy Huber, S. P.; Gullikson, E.; Meyer-Ilse, J. Journal of Materials Chemistry A, Vol. 5, Issue 12 https://doi.org/10.1039/C6TA10935G	journal	January 2017
Model oxide supported MoS2 HDS catalysts: structure and surface properties Cesano, Federico; Bertarione, Serena; Piovano, Andrea Catalysis Science & Technology, Vol. 1, Issue 1 https://doi.org/10.1039/c0cy00050g	journal	January 2011
Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts Merki, Daniel; Hu, Xile Energy & Environmental Science, Vol. 4, Issue 10, 3878 https://doi.org/10.1039/c1ee01970h	journal	January 2011
Fe, Co, and Ni ions promote the catalytic activity of amorphous molybdenum sulfide films for hydrogen evolution Merki, Daniel; Vrubel, Heron; Rovelli, Lorenzo Chemical Science, Vol. 3, Issue 8 https://doi.org/10.1039/c2sc20539d	journal	January 2012
XAFS in dilute magnetic semiconductors Sun, Zhihu; Yan, Wensheng; Yao, Tao Dalton Transactions, Vol. 42, Issue 38 https://doi.org/10.1039/c3dt50888a	journal	January 2013
Synthesis of novel CoC _x @C nanoparticles Chen, Liliang; Mashimo, Tsutomu; Iwamoto, Chihiro Nanotechnology, Vol. 24, Issue 4 https://doi.org/10.1088/0957-4484/24/4/045602	journal	January 2013
Identification of Active Edge Sites for Electrochemical H₂ Evolution from MoS₂ Nanocatalysts Jaramillo, T. F.; Jorgensen, K. P.; Bonde, J. Science, Vol. 317, Issue 5834, p. 100-102 https://doi.org/10.1126/science.1141483	journal	July 2007
Recent advances in unveiling active sites in molybdenum sulfide-based electrocatalysts for the hydrogen evolution reaction Seo, Bora; Joo, Sang Hoon Nano Convergence, Vol. 4, Issue 1 https://doi.org/10.1186/s40580-017-0112-3	journal	July 2017

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Tree-Like NiS2/MoS2-RGO Nanocomposites as pH Universal Electrocatalysts for Hydrogen Evolution Reaction Wang, Lina; Guo, Tong; Sun, Sen Catalysis Letters, Vol. 149, Issue 5 https://doi.org/10.1007/s10562-019-02698-7	journal	February 2019
Defect engineering of molybdenum disulfide through ion irradiation to boost hydrogen evolution reaction performance Sun, Cheng; Wang, Peipei; Wang, Hao Nano Research, Vol. 12, Issue 7 https://doi.org/10.1007/s12274-019-2400-1	journal	April 2019
The preparation of Ni/Mo-based ternary electrocatalysts by the self-propagating initiated nitridation reaction and their application for efficient hydrogen production Hou, Mengjie; Lan, Ruyue; Hu, Zhibiao Nanoscale, Vol. 11, Issue 36 https://doi.org/10.1039/c9nr05358a	journal	January 2019
Active site manipulation in MoS ₂ cluster electrocatalysts by transition metal doping Humphrey, Jo J. L.; Kronberg, Rasmus; Cai, Rongsheng Nanoscale, Vol. 12, Issue 7 https://doi.org/10.1039/c9nr10702a	journal	January 2020
Ru _x Se@MoS ₂ hybrid as a highly efficient electrocatalyst toward hydrogen evolution reaction Chen, Qi; Wang, Kefeng; Qin, Jingjing RSC Advances, Vol. 9, Issue 24 https://doi.org/10.1039/c9ra02873k	journal	January 2019
NO reduction over an Al-embedded MoS ₂ monolayer: a first-principles study Esrafili, Mehdi D.; Heydari, Safa RSC Advances, Vol. 9, Issue 67 https://doi.org/10.1039/c9ra05759e	journal	January 2019
Superior electrocatalytic hydrogen evolution at engineered non-stoichiometric two-dimensional transition metal dichalcogenide edges Hu, Guoxiang; Fung, Victor; Sang, Xiahan Journal of Materials Chemistry A, Vol. 7, Issue 31 https://doi.org/10.1039/c9ta05546k	journal	January 2019

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