Solid-state synthesis of MoS2 nanorod from molybdenum-organic framework for efficient hydrogen evolution reaction

  • Jun-Dong Yi (伊俊东)
  • Tao-Tao Liu (刘陶陶)
  • Yuan-Biao Huang (黄远标)Email author
  • Rong Cao (曹荣)Email author


MoS2 is a promising candidate for catalyzing hydrogen evolution reaction (HER) due to its low cost and high activity. However, the poor conductivity and the stack of active sites of bulk MoS2 hinder its application. Herein, a new facile solid-state synthesis strategy was developed to fabricate MoS2 nanorods by one-step pyrolysis of molybdenum-organic framework (Mo-MOF) in the presence of thiourea. The obtained MoS2 keeps the Mo-MOF nanorod structure with more active sites, while the residual carbon left in the nanorod enhances the conductivity. The as-prepared MoS2 nanorods exhibit superior stability and excellent activity towards HER with a small onset potential of 96 mV and a low Tafel slope of 93 mV decade−1.


metal-organic framework MoS2 nanorod hydrogen evolution reaction 



在电解水产氢反应(HER)中, 为了替代传统使用的价格高昂的铂基催化剂, 开发含量丰富、高效的非贵金属催化剂是近年来的研究 热点. 这其中, 二硫化钼(MoS2)由于其低廉的成本和良好的活性受到了广泛的关注. 目前, 大多数报导均使用水热法合成MoS2, 很少使用固 相法合成MoS2. 本文, 我们使用一种钼基金属有机框架作为牺牲模板, 通过一步高温固相合成得到尺寸均匀的MoS2纳米棒. 所得棒状形貌 能够有效暴露MoS2边缘活性位点, 提升HER活性. 同时, 固相合成后, 材料中仍有少量碳残留, 这些残余的碳提升了催化剂的导电性, 加速 了HER过程中的电子转移,提升了催化剂的反应活性. 因此我们合成的MoS2纳米棒表现出优异的HER性能, 拥有很小的起始电位(96 mV) 以及很低的塔菲尔斜率(93 mV dec−1). 本工作为固相合成基于MoS2的复合材料提供了一种新的思路.



We acknowledge the financial support from the National Key Research and Development Program of China (2017YFA0700100 and 2018YFA0208600), Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), National Natural Science Foundation of China (21671188, 21871263 and 21331006), Key Research Program of Frontier Science, CAS (QYZDJSSW- SLH045) and Youth Innovation Promotion Association, CAS (2014265).

Supplementary material

40843_2018_9393_MOESM1_ESM.pdf (4.4 mb)
Solid-state synthesis of MoS2 nanorod from molybdenum-organic framework for efficient hydrogen evolution reaction


  1. 1.
    Dresselhaus MS, Thomas IL. Alternative energy technologies. Nature, 2001, 414: 332–337Google Scholar
  2. 2.
    Chu S, Majumdar A. Opportunities and challenges for a sustainable energy future. Nature, 2012, 488: 294–303Google Scholar
  3. 3.
    Turner JA. Sustainable hydrogen production. Science, 2004, 305: 972–974Google Scholar
  4. 4.
    Mallouk TE. Water electrolysis: divide and conquer. Nat Chem, 2013, 5: 362–363Google Scholar
  5. 5.
    Zou X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting. Chem Soc Rev, 2015, 44: 5148–5180Google Scholar
  6. 6.
    Morales-Guio CG, Stern LA, Hu X. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem Soc Rev, 2014, 43: 6555Google Scholar
  7. 7.
    Li P, Yang Z, Shen J, et al. Subnanometer molybdenum sulfide on carbon nanotubes as a highly active and stable electrocatalyst for hydrogen evolution reaction. ACS Appl Mater Interfaces, 2016, 8: 3543–3550Google Scholar
  8. 8.
    Zhu B, Zou R, Xu Q. Metal-organic framework based catalysts for hydrogen evolution. Adv Energy Mater, 2018, 8: 1801193Google Scholar
  9. 9.
    Tabassum H, Guo W, Meng W, et al. Metal-organic frameworks derived cobalt phosphide architecture encapsulated into B/N codoped graphene nanotubes for all pH value electrochemical hydrogen evolution. Adv Energy Mater, 2017, 7: 1601671Google Scholar
  10. 10.
    Yan H, Xie Y, Jiao Y, et al. Holey reduced graphene oxide coupled with an Mo2N-Mo2C heterojunction for efficient hydrogen evolution. Adv Mater, 2017, 30: 1704156Google Scholar
  11. 11.
    Wu A, Xie Y, Ma H, et al. Integrating the active OER and HER components as the heterostructures for the efficient overall water splitting. Nano Energy, 2018, 44: 353–363Google Scholar
  12. 12.
    Chen W, Pei J, He CT, et al. Rational design of single molybdenum atoms anchored on N-doped carbon for effective hydrogen evolution reaction. Angew Chem Int Ed, 2017, 56: 16086–16090Google Scholar
  13. 13.
    Wang H, Min S, Wang Q, et al. Nitrogen-doped nanoporous carbon membranes with Co/CoP Janus-type nanocrystals as hydrogen evolution electrode in both acidic and alkaline environments. ACS Nano, 2017, 11: 4358–4364Google Scholar
  14. 14.
    Zhang FS, Wang JW, Luo J, et al. Extraction of nickel from NiFe-LDH into Ni2P@NiFe hydroxide as a bifunctional electrocatalyst for efficient overall water splitting. Chem Sci, 2018, 9: 1375–1384Google Scholar
  15. 15.
    Hinnemann B, Moses PG, Bonde J, et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J Am Chem Soc, 2005, 127: 5308–5309Google Scholar
  16. 16.
    Xie J, Zhang H, Li S, et al. Defect-rich MoS2 ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution. Adv Mater, 2013, 25: 5807–5813Google Scholar
  17. 17.
    Guo Y, Tang J, Qian H, et al. One-pot synthesis of zeolitic imidazolate framework 67-derived hollow Co3S4@MoS2 heterostructures as efficient bifunctional catalysts. Chem Mater, 2017, 29: 5566–5573Google Scholar
  18. 18.
    Meng C, Liu Z, Zhang T, et al. Layered MoS2 nanoparticles on TiO2 nanotubes by a photocatalytic strategy for use as high-performance electrocatalysts in hydrogen evolution reactions. Green Chem, 2015, 17: 2764–2768Google Scholar
  19. 19.
    Zhao Z, Qin F, Kasiraju S, et al. Vertically aligned MoS2/Mo2C hybrid nanosheets grown on carbon paper for efficient electrocatalytic hydrogen evolution. ACS Catal, 2017, 7: 7312–7318Google Scholar
  20. 20.
    Zheng X, Xu J, Yan K, et al. Space-confined growth of MoS2 nanosheets within graphite: the layered hybrid of MoS2 and graphene as an active catalyst for hydrogen evolution reaction. Chem Mater, 2014, 26: 2344–2353Google Scholar
  21. 21.
    Hu WH, Han GQ, Dai FN, et al. Effect of pH on the growth of MoS2 (002) plane and electrocatalytic activity for HER. Int J Hydrogen Energy, 2016, 41: 294–299Google Scholar
  22. 22.
    Shang X, Hu WH, Li X, et al. Oriented stacking along vertical (002) planes of MoS2: a novel assembling style to enhance activity for hydrogen evolution. Electrochim Acta, 2017, 224: 25–31Google Scholar
  23. 23.
    Hu WH, Shang X, Xue J, et al. Activating MoS2/CNs by tuning (001) plane as efficient electrocatalysts for hydrogen evolution reaction. Int J Hydrogen Energy, 2017, 42: 2088–2095Google Scholar
  24. 24.
    Liu Y, Zhou X, Ding T, et al. 3D architecture constructed via the confined growth of MoS2 nanosheets in nanoporous carbon derived from metal–organic frameworks for efficient hydrogen production. Nanoscale, 2015, 7: 18004–18009Google Scholar
  25. 25.
    Voiry D, Salehi M, Silva R, et al. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett, 2013, 13: 6222–6227Google Scholar
  26. 26.
    Toh RJ, Sofer Z, Luxa J, et al. 3R phase of MoS2 and WS2 outperforms the corresponding 2H phase for hydrogen evolution. Chem Commun, 2017, 53: 3054–3057Google Scholar
  27. 27.
    Ren X, Ma Q, Fan H, et al. A Se-doped MoS2 nanosheet for improved hydrogen evolution reaction. Chem Commun, 2015, 51: 15997–16000Google Scholar
  28. 28.
    Wang H, Tsai C, Kong D, et al. Transition-metal doped edge sites in vertically aligned MoS2 catalysts for enhanced hydrogen evolution. Nano Res, 2015, 8: 566–575Google Scholar
  29. 29.
    Li Y, Wang H, Xie L, et al. MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. J Am Chem Soc, 2011, 133: 7296–7299Google Scholar
  30. 30.
    Zhou W, Zhou K, Hou D, et al. Three-dimensional hierarchical frameworks based on MoS2 nanosheets self-assembled on graphene oxide for efficient electrocatalytic hydrogen evolution. ACS Appl Mater Interfaces, 2014, 6: 21534–21540Google Scholar
  31. 31.
    Zhu H, Du ML, Zhang M, et al. S-rich single-layered MoS2 nanoplates embedded in N-doped carbon nanofibers: efficient coelectrocatalysts for the hydrogen evolution reaction. Chem Commun, 2014, 50: 15435–15438Google Scholar
  32. 32.
    Zhang G, Liu H, Qu J, et al. Two-dimensional layered MoS2: rational design, properties and electrochemical applications. Energy Environ Sci, 2016, 9: 1190–1209Google Scholar
  33. 33.
    Zhou HC, Long JR, Yaghi OM. Introduction to metal–organic frameworks. Chem Rev, 2012, 112: 673–674Google Scholar
  34. 34.
    Zhou HC, Kitagawa S. Metal–organic frameworks (MOFs). Chem Soc Rev, 2014, 43: 5415–5418Google Scholar
  35. 35.
    Zhu QL, Xu Q. Metal–organic framework composites. Chem Soc Rev, 2014, 43: 5468–5512Google Scholar
  36. 36.
    Cook TR, Zheng YR, Stang PJ. Metal–organic frameworks and selfassembled supramolecular coordination complexes: comparing and contrasting the design, synthesis, and functionality of metal–organic materials. Chem Rev, 2012, 113: 734–777Google Scholar
  37. 37.
    Fang Z, Bueken B, De Vos DE, et al. Defect-engineered metalorganic frameworks. Angew Chem Int Ed, 2015, 54: 7234–7254Google Scholar
  38. 38.
    Xia W, Mahmood A, Zou R, et al. Metal–organic frameworks and their derived nanostructures for electrochemical energy storage and conversion. Energy Environ Sci, 2015, 8: 1837–1866Google Scholar
  39. 39.
    Mahmood A, Guo W, Tabassum H, et al. Metal-organic framework-based nanomaterials for electrocatalysis. Adv Energy Mater, 2016, 6: 1600423Google Scholar
  40. 40.
    Liang Z, Qu C, Guo W, et al. Pristine metal-organic frameworks and their composites for energy storage and conversion. Adv Mater, 2018, 30: 1702891Google Scholar
  41. 41.
    Zhang H, Osgood H, Xie X, et al. Engineering nanostructures of PGM-free oxygen-reduction catalysts using metal-organic frameworks. Nano Energy, 2017, 31: 331–350Google Scholar
  42. 42.
    Cao X, Zheng B, Shi W, et al. Reduced graphene oxide-wrapped MoO3 composites prepared by using metal-organic frameworks as precursor for all-solid-state flexible supercapacitors. Adv Mater, 2015, 27: 4695–4701Google Scholar
  43. 43.
    Zhao X, Zhu H, Yang X. Amorphous carbon supported MoS2 nanosheets as effective catalysts for electrocatalytic hydrogen evolution. Nanoscale, 2014, 6: 10680–10685Google Scholar
  44. 44.
    Srivastava SK, Kartick B, Choudhury S, et al. Thermally fabricated MoS2-graphene hybrids as high performance anode in lithium ion battery. Mater Chem Phys, 2016, 183: 383–391Google Scholar
  45. 45.
    Wan Z, Shao J, Yun J, et al. Core-shell structure of hierarchical quasi-hollow MoS2 microspheres encapsulated porous carbon as stable anode for Li-ion batteries. Small, 2014, 10: 4975–4981Google Scholar
  46. 46.
    Yi JD, Shi PC, Liang J, et al. Porous hollow MoS2 microspheres derived from core–shell sulfonated polystyrene microspheres@ MoS2 nanosheets for efficient electrocatalytic hydrogen evolution. Inorg Chem Front, 2017, 4: 741–747Google Scholar
  47. 47.
    Bian H, Ji Y, Yan J, et al. In situ synthesis of few-layered g-C3N4 with vertically aligned MoS2 loading for boosting solar-to-hydrogen generation. Small, 2018, 14: 1703003Google Scholar
  48. 48.
    Wang H, Lu Z, Kong D, et al. Electrochemical tuning of MoS2 nanoparticles on three-dimensional substrate for efficient hydrogen evolution. ACS Nano, 2014, 8: 4940–4947Google Scholar
  49. 49.
    Zhang Z, Li W, Yuen MF, et al. Hierarchical composite structure of few-layers MoS2 nanosheets supported by vertical graphene on carbon cloth for high-performance hydrogen evolution reaction. Nano Energy, 2015, 18: 196–204Google Scholar
  50. 50.
    Khalid M, Honorato AMB, Varela H, et al. Multifunctional electrocatalysts derived from conducting polymer and metal organic framework complexes. Nano Energy, 2018, 45: 127–135Google Scholar
  51. 51.
    Xia BY, Yan Y, Li N, et al. A metal–organic framework-derived bifunctional oxygen electrocatalyst. Nat Energy, 2016, 1: 15006Google Scholar
  52. 52.
    Chen R, Yang C, Cai W, et al. Use of platinum as the counter electrode to study the activity of nonprecious metal catalysts for the hydrogen evolution reaction. ACS Energy Lett, 2017, 2: 1070–1075Google Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Jun-Dong Yi (伊俊东)
    • 1
  • Tao-Tao Liu (刘陶陶)
    • 1
    • 2
  • Yuan-Biao Huang (黄远标)
    • 1
    • 2
    Email author
  • Rong Cao (曹荣)
    • 1
    • 2
    Email author
  1. 1.State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouChina
  2. 2.University of Chinese Academy of SciencesBeijingChina

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