Science China Materials

, Volume 60, Issue 9, pp 849–856 | Cite as

Defective MoS2 electrocatalyst for highly efficient hydrogen evolution through a simple ball-milling method

  • Li-Fang Zhang (张丽芳)
  • Xiaoxing Ke (柯小行)
  • Gang Ou (欧刚)
  • Hehe Wei (魏呵呵)
  • Lu-Ning Wang (王鲁宁)Email author
  • Hui Wu (伍晖)Email author


Molybdenum disulfide (MoS2) has attracted extensive attention as an alternative to replace noble electrocatalysts in the hydrogen evolution reaction (HER). Here, we highlight an efficient and straightforward ball milling method, using nanoscale Cu powders as reductant to reduce MoS2 engineering S-vacancies into MoS2 surfaces, to fabricate a defectrich MoS2 material (DR-MoS2). The micron-sized DR-MoS2 catalysts exhibit significantly enhanced catalytic activity for HER with an overpotential (at 10 mA cm−2) of 176 mV in acidic media and 189 mV in basic media, surpassing most of Mo-based catalysts previously reported, especially in basic solution. Meanwhile stability tests confirm the outstanding durability of DR-MoS2 catalysts in both acid and basic electrolytes. This work not only opens a new pathway to implant defects to MoS2, but also provides low-cost alternative for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.


electrocatalyst hydrogen evolution MoS2 defects S-vacancies 



通过电催化将水分解可大量制备高纯度氢气, 这一过程需要高效能低成本的电催化剂材料. 二硫化钼价格低廉、 资源丰富, 且具有类似贵金属铂的氢吸附自由能, 是一种潜在的高效制氢电催化剂. 然而其仍面临着析氢过电位偏高、 稳定性差、 难以批量制备、 在碱性环境下催化析氢活性较低等问题, 限制了其实际应用. 目前, 大量文献证实制造缺陷是一种有效的优化二硫化钼电催化活性的方法. 本文通过球磨还原法制备了一种富含缺陷的二硫化钼析氢反应电催化剂. 这种新型的富缺陷二硫化钼催化剂在酸碱性条件下都显示出较高的催化活性, 在酸性条件下, 过电位为176 mV时其电流密度可达10 mA cm−2; 在碱性条件下, 过电位为189 mV时其电流密度可达10 mA cm−2, 超过了大部分报道的析氢反应电催化剂. 此外, 富缺陷二硫化钼材料显示出较小的塔菲尔斜率和良好的电化学稳定性, 进一步证实了析氢反应催化活性的增强. 这种通过球磨还原制造缺陷的思路为未来催化剂的设计与性能优化开辟了一条新的道路, 且该方法简单, 适于大规模的工业生产.



This work was supported by the National Basic Research of China (2015CB932500 and 2013CB632702) and the National Natural Science Fundation of China (51302141, 51501008, U1560103 and 61274015).

Supplementary material

40843_2017_9086_MOESM1_ESM.pdf (1.4 mb)
Defective MoS2 electrocatalyst for highly efficient hydrogen evolution through a simple ball-milling method


  1. 1.
    Chen HM, Chen CK, Liu RS, et al. Nano-architecture and material designs for water splitting photoelectrodes. Chem Soc Rev, 2012, 41: 5654–5671CrossRefGoogle Scholar
  2. 2.
    Zou X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting. Chem Soc Rev, 2015, 44: 5148–5180CrossRefGoogle Scholar
  3. 3.
    Lu S, Zhuang Z. Electrocatalysts for hydrogen oxidation and evolution reactions. Sci China Mater, 2016, 59: 217–238CrossRefGoogle Scholar
  4. 4.
    Jiao Y, Zheng Y, Jaroniec M, et al. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem Soc Rev, 2015, 44: 2060–2086CrossRefGoogle Scholar
  5. 5.
    Stamenkovic VR, Mun BS, Arenz M, et al. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat Mater, 2007, 6: 241–247CrossRefGoogle Scholar
  6. 6.
    Yang H, Wang C, Hu F, et al. Atomic-scale Pt clusters decorated on porous α-Ni(OH)2 nanowires as highly efficient electrocatalyst for hydrogen evolution reaction. Sci China Mater, 2017Google Scholar
  7. 7.
    Morales-Guio CG, Stern LA, Hu X. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem Soc Rev, 2014, 43: 6555–6569CrossRefGoogle Scholar
  8. 8.
    Chen WF, Sasaki K, Ma C, et al. Hydrogen-evolution catalysts based on non-noble metal nickel-molybdenum nitride nanosheets. Angew Chem Int Ed, 2012, 51: 6131–6135CrossRefGoogle Scholar
  9. 9.
    Lu Q, Hutchings GS, Yu W, et al. Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution. Nat Commun, 2015, 6: 6567–6574CrossRefGoogle Scholar
  10. 10.
    Xu X, Chen Y, Zhou W, et al. A perovskite electrocatalyst for efficient hydrogen evolution reaction. Adv Mater, 2016, 28: 6442–6448CrossRefGoogle Scholar
  11. 11.
    Chen P, Xu K, Tao S, et al. Phase-transformation engineering in cobalt diselenide realizing enhanced catalytic activity for hydrogen evolution in an alkaline medium. Adv Mater, 2016, 28: 7527–7532CrossRefGoogle Scholar
  12. 12.
    Xing Z, Liu Q, Asiri AM, et al. Closely interconnected network of molybdenum phosphide nanoparticles: a highly efficient electrocatalyst for generating hydrogen from water. Adv Mater, 2014, 26: 5702–5707CrossRefGoogle Scholar
  13. 13.
    Tang C, Cheng N, Pu Z, et al. NiSe nanowire film supported on nickel foam: an efficient and stable 3D bifunctional electrode for full water splitting. Angew Chem Int Ed, 2015, 54: 9351–9355CrossRefGoogle Scholar
  14. 14.
    Yang Y, Xu X, Wang X. Synthesis of Mo-based nanostructures from organic-inorganic hybrid with enhanced electrochemical for water splitting. Sci China Mater, 2015, 58: 775–784CrossRefGoogle Scholar
  15. 15.
    Zeng M, Li Y. Recent advances in heterogeneous electrocatalysts for the hydrogen evolution reaction. J Mater Chem A, 2015, 3: 14942–14962CrossRefGoogle Scholar
  16. 16.
    Ge X, Chen L, Zhang L, et al. Nanoporous metal enhanced catalytic activities of amorphous molybdenum sulfide for high-efficiency hydrogen production. Adv Mater, 2014, 26: 3100–3104CrossRefGoogle Scholar
  17. 17.
    Ji Q, Zhang Y, Shi J, et al. Morphological engineering of CVDgrown transition metal dichalcogenides for efficient electrochemical hydrogen evolution. Adv Mater, 2016, 28: 6207–6212CrossRefGoogle Scholar
  18. 18.
    Yang X, Li Q, Hu G, et al. Controlled synthesis of high-quality crystals of monolayer MoS2 for nanoelectronic device application. Sci China Mater, 2016, 59: 182–190CrossRefGoogle Scholar
  19. 19.
    Chhowalla M, Shin HS, Eda G, et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat Chem, 2013, 5: 263–275CrossRefGoogle Scholar
  20. 20.
    Hinnemann B, Moses PG, Bonde J, et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J Am Chem Soc, 2005, 127: 5308–5309CrossRefGoogle Scholar
  21. 21.
    Chen Z, Cummins D, Reinecke BN, et al. Core–shell MoO3–MoS2 nanowires for hydrogen evolution: a functional design for electrocatalytic materials. Nano Lett, 2011, 11: 4168–4175CrossRefGoogle Scholar
  22. 22.
    Lu Q, Yu Y, Ma Q, et al. 2D transition-metal-dichalcogenide-nanosheet- based composites for photocatalytic and electrocatalytic hydrogen evolution reactions. Adv Mater, 2016, 28: 1917–1933CrossRefGoogle Scholar
  23. 23.
    Liu S, Zhang X, Zhang J, et al. MoS2 with tunable surface structure directed by thiophene adsorption toward HDS and HER. Sci China Mater, 2016, 59: 1051–1061CrossRefGoogle Scholar
  24. 24.
    Liu J, Cao H, Jiang B, et al. Newborn 2D materials for flexible energy conversion and storage. Sci China Mater, 2016, 59: 459–474Google Scholar
  25. 25.
    Zhou W, Zou X, Najmaei S, et al. Intrinsic structural defects in monolayer molybdenum disulfide. Nano Lett, 2013, 13: 2615–2622CrossRefGoogle Scholar
  26. 26.
    Liao L, Zhu J, Bian X, et al. MoS2 formed on mesoporous graphene as a highly active catalyst for hydrogen evolution. Adv Funct Mater, 2013, 23: 5326–5333CrossRefGoogle Scholar
  27. 27.
    Ouyang Y, Ling C, Chen Q, et al. Activating inert basal planes of MoS2 for hydrogen evolution reaction through the formation of different intrinsic defects. Chem Mater, 2016, 28: 4390–4396CrossRefGoogle 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: 566–575CrossRefGoogle Scholar
  29. 29.
    Kong D, Wang H, Cha JJ, et al. Synthesis of MoS2 and MoSe2 films with vertically aligned layers. Nano Lett, 2013, 13: 1341–1347CrossRefGoogle Scholar
  30. 30.
    Wang T, Liu L, Zhu Z, et al. Enhanced electrocatalytic activity for hydrogen evolution reaction from self-assembled monodispersed molybdenum sulfidenanoparticles on an Au electrode. Energ Environ Sci, 2013, 6: 625–633CrossRefGoogle Scholar
  31. 31.
    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: 5807–5813CrossRefGoogle Scholar
  32. 32.
    Ataca C, Ciraci S. Dissociation of H2O at the vacancies of singlelayer MoS2. Phys Rev B, 2012, 85: 195410CrossRefGoogle Scholar
  33. 33.
    Li H, Du M, Mleczko MJ, et al. Kinetic study of hydrogen evolution reaction over strained MoS2 with sulfur vacancies using scanning electrochemical microscopy. J Am Chem Soc, 2016, 138: 5123–5129CrossRefGoogle Scholar
  34. 34.
    Li H, Tsai C, Koh AL, et al. Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. Nat Mater, 2016, 15: 48–53CrossRefGoogle Scholar
  35. 35.
    Lukowski MA, Daniel AS, Meng F, et al. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. J Am Chem Soc, 2013, 135: 10274–10277CrossRefGoogle Scholar
  36. 36.
    Merki D, Hu X. Recent developments of molybdenum and tungsten sulfides as hydrogen evolution catalysts. Energ Environ Sci, 2011, 4: 3878–3888CrossRefGoogle Scholar
  37. 37.
    Staszak-Jirkovský J, Malliakas CD, Lopes PP, et al. Design of active and stable Co–Mo–Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction. Nat Mater, 2016, 15: 197–203CrossRefGoogle Scholar
  38. 38.
    Kang N, Paudel HP, Leuenberger MN, et al. Photoluminescence quenching in single-layer MoS2 via oxygen plasma treatment. J Phys Chem C, 2014, 118: 21258–21263CrossRefGoogle Scholar
  39. 39.
    Ye TN, Lv LB, Xu M, et al. Hierarchical carbon nanopapers coupled with ultrathin MoS2 nanosheets: highly efficient large-area electrodes for hydrogen evolution. Nano Energ, 2015, 15: 335–342CrossRefGoogle Scholar
  40. 40.
    Kiriya D, Lobaccaro P, Nyein HYY, et al. General thermal texturization process of MoS2 for efficient electrocatalytic hydrogen evolution reaction. Nano Lett, 2016, 16: 4047–4053CrossRefGoogle Scholar
  41. 41.
    Benck JD, Chen Z, Kuritzky LY, et al. Amorphous molybdenum sulfide catalysts for electrochemical hydrogen production: insights into the origin of their catalytic activity. ACS Catal, 2012, 2: 1916–1923CrossRefGoogle Scholar
  42. 42.
    Kibsgaard J, Chen Z, Reinecke BN, et al. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat Mater, 2012, 11: 963–969CrossRefGoogle Scholar
  43. 43.
    Vrubel H, Hu X. Molybdenum boride and carbide catalyze hydrogen evolution in both acidic and basic solutions. Angew Chem, 2012, 124: 12875–12878CrossRefGoogle Scholar
  44. 44.
    Zou X, Huang X, Goswami A, et al. Cobalt-embedded nitrogenrich carbon nanotubes efficiently catalyze hydrogen evolution reaction at all pH values. Angew Chem, 2014, 126: 4461–4465CrossRefGoogle Scholar
  45. 45.
    Merki D, Fierro S, Vrubel H, et al. Amorphous molybdenum sulfide films as catalysts for electrochemical hydrogen production in water. Chem Sci, 2011, 2: 1262–1267CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2017

Authors and Affiliations

  • Li-Fang Zhang (张丽芳)
    • 1
    • 2
  • Xiaoxing Ke (柯小行)
    • 3
  • Gang Ou (欧刚)
    • 2
  • Hehe Wei (魏呵呵)
    • 2
  • Lu-Ning Wang (王鲁宁)
    • 1
    Email author
  • Hui Wu (伍晖)
    • 2
    Email author
  1. 1.School of Materials Science and EngineeringUniversity of Science and Technology BeijingBeijingChina
  2. 2.School of Materials Science and EngineeringTsinghua UniversityBeijingChina
  3. 3.Institute of Microstructure and Property of Advanced MaterialsBeijing University of TechnologyBeijingChina

Personalised recommendations