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Research Article

Unsaturated-sulfur-rich MoS2 nanosheets decorated on free-standing SWNT film: Synthesis, characterization and electrocatalytic application

Daobin Liu1, Weiyu Xu1, Qin Liu1, Qun He1, Yasir A. Haleem1, Changda Wang1, Ting Xiang1, Chongwen Zou1, Wangsheng Chu1, Jun Zhong2, Zhiqiang Niu2, Li Song1,3( )
National Synchrotron Radiation LaboratoryCAS Hefei Science CenterUniversity of Science and Technology of ChinaHefei230029China
Jiangsu Key Laboratory for Carbon-Based Functional Materials & DevicesInstitute of Functional Nano & Soft Materials Laboratory (FUNSOM)Soochow UniversitySuzhou215123China
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education)College of ChemistryCollaborative Innovation Center of Chemical Science and EngineeringNankai UniversityTianjin300071China
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Abstract

Herein, we report a bottom-up solvothermal route to synthesize a flexible, highly efficient MoS2@SWNT electrocatalyst for hydrogen evolution reactions (HER). Characterization revealed that branch-like MoS2 nanosheets containing sulfurrich sites were in situ uniformly dispersed on free-standing single-walled carbon nanotube (SWNT) film, which could expose more unsaturated sulfur atoms, allowing excellent electrical contact with active sites. The flexible catalyst exhibited excellent HER performance with a low overpotential (~150 mV at 10 mA/cm2) and small Tafel slope (41 mV/dec). To further explain the improved performance, the local electronic structure was investigated by X-ray absorption near-edge structure (XANES) analysis, proving the presence of unsaturated sulfur atoms and strong electronic coupling between MoS2 and SWNT. This study provides an in-situ synthetic route to create new multifunctional flexible hybridized catalysts and useful insights into the relationships among the catalyst microstructure, electronic structure, and properties.

Keywords

unsaturated-sulfur-richMoS2 flexibleX-ray absorption near-edge structurehydrogen evolution

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References

1

Turner, J. A. Sustainable hydrogen production. Science 2004, 305, 972–974.
Crossref Google Scholar
2

Mavrikakis, M. Computational methods: A search engine for catalysts. Nat. Mater. 2006, 5, 847–848.
Crossref Google Scholar
3

Mallouk, T. E. Water electrolysis: Divide and conquer. Nat. Chem. 2013, 5, 362–363.
Crossref Google Scholar
4

Greeley, J.; Jaramillo, T. F.; Bonde, J.; Chorkendorff, I.; Nørskov, J. K. Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater. 2006, 5, 909–913.
Crossref Google Scholar
5

Duan, J. J.; Chen, S.; Jaroniec, M.; Qiao, S. Z. Porous C3N4 nanolayers@N-graphene films as catalyst electrodes for highly efficient hydrogen evolution. ACS Nano 2015, 9, 931–940.
Crossref Google Scholar
6

Norskov, J. K.; Christensen, C. H. Toward efficient hydrogen production at surfaces. Science 2006, 312, 1322–1323.
Crossref Google Scholar
7

Merki, D.; Hu, X. L. Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts. Energy Environ. Sci. 2011, 4, 3878–3888.
Crossref Google Scholar
8

Laursen, A. B.; Kegnæs, S.; Dahl, S.; Chorkendorff, I. Molybdenum sulfides-efficient and viable materials for electro- and photoelectrocatalytic hydrogen evolution. Energy Environ. Sci. 2012, 5, 5577–5591.
Crossref Google Scholar
9

Eda, G.; Fujita, T.; Yamaguchi, H.; Voiry, D.; Chen, M. W.; Chhowalla, M. Coherent atomic and electronic heterostructures of single-layer MoS2. ACS Nano 2012, 6, 7311–7317.
Crossref Google Scholar
10

Lukowski, M. A.; Daniel, A. S.; Meng, F.; Forticaux, A.; Li, L. S.; Jin, S. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. J. Am. Chem. Soc. 2013, 135, 10274–10277.
Crossref Google Scholar
11

Jaramillo, T. F.; Jørgensen, K. P.; Bonde, J.; Nielsen, J. H.; Horch, S.; Chorkendorff, I. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 2007, 317, 100–102.
Crossref Google Scholar
12

Chou, S. S.; De, M.; Kim, J.; Byun, S.; Dykstra, C.; Yu, J.; Huang, J. X.; Dravid, V. P. Ligand conjugation of chemically exfoliated MoS2. J. Am. Chem. Soc. 2013, 135, 4584–4587.
Crossref Google Scholar
13

Chung, D. Y.; Park, S. K.; Chung, Y. H.; Yu, S. H.; Lim, D. H.; Jung, N.; Ham, H. C.; Park, H. Y.; Piao, Y. Z.; Yoo, S. J. et al. Edge-exposed MoS2 nano-assembled structures as efficient electrocatalysts for hydrogen evolution reaction. Nanoscale 2014, 6, 2131–2136.
Crossref Google Scholar
14

Voiry, D.; Salehi, M.; Silva, R.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G.; Chhowalla, M. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett. 2013, 13, 6222–6227.
Crossref Google Scholar
15

Xie, J. F.; Zhang, H.; Li, S.; Wang, R. X.; Sun, X.; Zhou, M.; Zhou, J. F.; Lou, X. W.; Xie, Y. Defect-rich MoS2 ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution. Adv. Mater. 2013, 25, 5807–5813.
Crossref Google Scholar
16

Kibsgaard, J.; Chen, Z. B.; Reinecke, B. N.; Jaramillo, T. F. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat. Mater. 2012, 11, 963–969.
Crossref Google Scholar
17

Yan, Y.; Xia, B. Y.; Ge, X. M.; Liu, Z. L.; Wang, J. Y.; Wang, X. Ultrathin MoS2 nanoplates with rich active sites as highly efficient catalyst for hydrogen evolution. ACS Appl. Mater. Interfaces 2013, 5, 12794–12798.
Crossref Google Scholar
18

Xie, J. F.; Zhang, J. J.; Li, S.; Grote, F.; Zhang, X. D.; Zhang, H.; Wang, R. X.; Lei, Y.; Pan, B. C.; Xie, Y. Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution. J. Am. Chem. Soc. 2013, 135, 17881–17888.
Crossref Google Scholar
19

Li, Y. G.; Wang, H. L.; Xie, L. M.; Liang, Y. Y.; Hong, G. S.; Dai, H. J. MoS2 nanoparticles grown on graphene: An advanced catalyst for the hydrogen evolution reaction. J. Am. Chem. Soc. 2011, 133, 7296–7299.
Crossref Google Scholar
20

Wang, H. T.; Tsai, C.; Kong, D. S.; Chan, K. R.; Abild- Pedersen, F.; Nørskov, J. K.; Cui, Y. Transition-metal doped edge sites in vertically aligned MoS2 catalysts for enhanced hydrogen evolution. Nano Res. 2015, 8, 566–575.
Crossref Google Scholar
21

Youn, D. H.; Jang, J. W.; Kim, J. Y.; Jang, J. S.; Choi, S. H.; Lee, J. S. Fabrication of graphene-based electrode in less than a minute through hybrid microwave annealing. Sci. Rep. 2014, 4, 5492.
Crossref Google Scholar
22

Zhao, X.; Zhu, H.; Yang, X. R. Amorphous carbon supported MoS2 nanosheets as effective catalysts for electrocatalytic hydrogen evolution. Nanoscale 2014, 6, 10680–10685.
Crossref Google Scholar
23

Liao, L.; Zhu, J.; Bian, X. J.; Zhu, L.; Scanlon, M. D.; Girault, H. H.; Liu, B. H. MoS2 formed on mesoporous graphene as a highly active catalyst for hydrogen evolution. Adv. Funct. Mater. 2013, 23, 5326–5333.
Crossref Google Scholar
24

Seo, B.; Jung, G. Y.; Sa, Y. J.; Jeong, H. Y.; Cheon, J. Y.; Lee, J. H.; Kim, H. Y.; Kim, J. C.; Shin, H. S.; Kwak, S. K. et al. Monolayer-precision synthesis of molybdenum sulfide nanoparticles and their nanoscale size effects in the hydrogen evolution reaction. ACS Nano 2015, 9, 3728–3739.
Crossref Google Scholar
25

Ye, T. -N.; Lv, L. -B.; Xu, M.; Zhang, B.; Wang, K. -X.; Su, J.; Li, X. -H.; Chen, J. -S. Hierarchical carbon nanopapers coupled with ultrathin MoS2 nanosheets: Highly efficient large-area electrodes for hydrogen evolution. Nano Energy 2015, 15, 335–342.
Crossref Google Scholar
26

Khan, M.; Yousaf, A. B.; Chen, M. M.; Wei, C. S.; Wu, X. B.; Huang, N. D.; Qi, Z. M.; Li, L. B. Molybdenum sulfide/graphene-carbon nanotube nanocomposite material for electrocatalytic applications in hydrogen evolution reactions. Nano Res. 2016, 9, 837–848.
Crossref Google Scholar
27

Song, L.; Ci, L.; Lv, L.; Zhou, Z.; Yan, X.; Liu, D.; Yuan, H.; Gao, Y.; Wang, J.; Liu, L. et al. Direct synthesis of a macroscale single-walled carbon nanotube non-woven material. Adv. Mater. 2004, 16, 1529–1534.
Crossref Google Scholar
28

Markovic, Z.; Kepic, D.; Antunovic, I. H.; Nikolic, M.; Dramicanin, M.; Cincovic, M. M.; Markovic, B. T. Raman study of single wall carbon nanotube thin films treated by laser irradiation and dynamic and isothermal oxidation. J. Raman Spectrosc. 2012, 43, 1413–1422.
Crossref Google Scholar
29

Shi, Y. M.; Wang, Y.; Wong, J. I.; Tan, A. Y. S.; Hsu, C. L.; Li, L. J.; Lu, Y. C.; Yang, H. Y. Self-assembly of hierarchical MoSx/CNT nanocomposites (2 < x < 3): Towards high performance anode materials for lithium ion batteries. Sci. Rep. 2013, 3, 2169.
Crossref
30

Buscema, M.; Steele, G. A.; van der Zant, H. S. J.; Castellanos-Gomez, A. The effect of the substrate on the Raman and photoluminescence emission of single-layer MoS2. Nano Res. 2014, 7, 561–571.
Crossref Google Scholar
31

Vrubel, H.; Merki, D.; Hu, X. L. Hydrogen evolution catalyzed by MoS3 and MoS2 particles. Energy Environ. Sci. 2012, 5, 6136–6144.
Crossref Google Scholar
32

Chang, Y. H.; Lin, C. T.; Chen, T. Y.; Hsu, C. L.; Lee, Y. H.; Zhang, W. J.; Wei, K. H.; Li, L. J. Highly efficient electrocatalytic hydrogen production by MoSx grown on grapheneprotected 3D Ni foams. Adv. Mater. 2013, 25, 756–760.
Crossref Google Scholar
33

Chen, Z. B.; Cummins, D.; Reinecke, B. N.; Clark, E.; Sunkara, M. K.; Jaramillo, T. F. Core–shell MoO3-MoS2 nanowires for hydrogen evolution: A functional design for electrocatalytic materials. Nano Lett. 2011, 11, 4168–4175.
Crossref Google Scholar
34

Sonntag, B.; Brown, F. C. Soft-X-ray response of transitionmetal layer compounds. Phys. Rev. B 1974, 10, 2300–2306.
Crossref Google Scholar
35

Didziulis, S. V.; Lince, J. R.; Shuh, D. K.; Durbin, T. D.; Yarmoff, J. A. Photoelectron spectroscopy of MoS2 at the sulfur 2p absorption edge. J. Electron Spectrosc. Relat. Phenom. 1992, 60, 175–192.
Crossref Google Scholar
36

Zhang, L.; Ji, L. W.; Glans, P. A.; Zhang, Y. G.; Zhu, J. F.; Guo, J. H. Electronic structure and chemical bonding of a graphene oxide-sulfur nanocomposite for use in superior performance lithium-sulfur cells. Phys. Chem. Chem. Phys. 2012, 14, 13670–13675.
Crossref Google Scholar
37

Ji, L. W.; Rao, M. M.; Zheng, H. M.; Zhang, L.; Li, Y. C.; Duan, W. H.; Guo, J. H.; Cairns, E. J.; Zhang, Y. G. Graphene oxide as a sulfur immobilizer in high performance lithium/ sulfur cells. J. Am. Chem. Soc. 2011, 133, 18522–18525.
Crossref Google Scholar
Nano Research
Volume 9 Issue 7,
July 2016
Pages 2079-2087
DOI: 10.1007/s12274-016-1098-6
Cite this article:
Liu D, Xu W, Liu Q, et al. Unsaturated-sulfur-rich MoS2 nanosheets decorated on free-standing SWNT film: Synthesis, characterization and electrocatalytic application. Nano Research, 2016, 9(7): 2079-2087. https://doi.org/10.1007/s12274-016-1098-6

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Received: 12 February 2016
Revised: 06 April 2016
Accepted: 08 April 2016
Published: 14 May 2016
© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2016
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