Skip to main content
SpringerLink
Log in

Targeted bottom-up synthesis of 1T-phase MoS2 arrays with high electrocatalytic hydrogen evolution activity by simultaneous structure and morphology engineering

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

The incorporation of small guest molecules or ions by bottom-up hydrothermal synthesis has recently emerged as a promising new way to engineer 1T-phase MoS2 with high hydrogen evolution reaction (HER) activity. However, the mechanism of the associated structural evolution remains elusive and controversial, leading to a lack of effective routes to prepare 1T-phase MoS2 with controlled structure and morphology, along with high purity and stability. Herein, urea is chosen as precursor of small molecules or ions to simultaneously engineer the phase (~16.4%, ~69.4%, and ~90.2% of 1T phase) and size (~98.8, ~151.6, and ~251.8 nm for the 90.2% 1T phase) of MoS2 nanosheets, which represent an ideal model system for investigating the structural evolution in these materials, as well as developing a new type of 1T-phase MoS2 arrays. Using reaction intermediate monitoring and theoretical calculations, we show that the oriented growth of 1T-phase MoS2 is controlled by ammonia-assisted assembly, recrystallization, and stabilization processes. A superior HER performance in acidic media is obtained, with an overpotential of only 76 mV required to achieve a stable current density of 10 mA·cm–2 for 15 h. This excellent performance is attributed to the unique array structure, involving well-dispersed, edge-terminated, and high-purity 1T-phase MoS2 nanosheets.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Wang, Q. H.; Kalantar-Zadeh, K.; Kis, A.; Coleman, J. N.; Strano, M. S. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat. Nano 2012, 7, 699–712.

    Article  Google Scholar 

  2. Jariwala, D.; Sangwan, V. K.; Lauhon, L. J.; Marks, T. J.; Hersam, M. C. Emerging device applications for semiconducting two-dimensional transition metal dichalcogenides. ACS Nano 2014, 8, 1102–1120.

    Article  Google Scholar 

  3. Lu, Q. P.; Yu, Y. F.; Ma, Q. L.; Chen, B.; Zhang, H. 2D transition-metal-dichalcogenide-nanosheet-based composites for photocatalytic and electrocatalytic hydrogen evolution reactions. Adv. Mater. 2016, 28, 1917–1933.

    Article  Google Scholar 

  4. Liu, D. B.; Xu, W. Y.; Liu, Q.; He, Q.; Haleem, Y. A.; Wang, C. D.; Xiang, T.; Zou, C. W.; Chu, W. S.; Zhong, J. et al. Unsaturated-sulfur-rich MoS2 nanosheets decorated on free-standing SWNT film: Synthesis, characterization and electrocatalytic application. Nano Res. 2016, 9, 2079–2087.

    Article  Google Scholar 

  5. 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.

    Article  Google Scholar 

  6. Ding, Q.; Song, B.; Xu, P.; Jin, S. Efficient electrocatalytic and photoelectrochemical hydrogen generation using MoS2 and related compounds. Chem 2016, 1, 699–726.

    Article  Google Scholar 

  7. Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L. J.; Loh, K. P.; Zhang, H. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 2013, 5, 263–275.

    Article  Google Scholar 

  8. Kong, D. S.; Wang, H. T.; Cha, J. J.; Pasta, M.; Koski, K. J.; Yao, J.; Cui, Y. Synthesis of MoS2 and MoSe2 films with vertically aligned layers. Nano Lett. 2013, 13, 1341–1347.

    Article  Google Scholar 

  9. Tan, Y. W.; Liu, P.; Chen, L. Y.; Cong, W. T.; Ito, Y.; Han, J. H.; Guo, X. W.; Tang, Z.; Fujita, T.; Hirata, A. et al. Monolayer MoS2 films supported by 3D nanoporous metals for high-efficiency electrocatalytic hydrogen production. Adv. Mater. 2014, 26, 8023–8028.

    Article  Google Scholar 

  10. 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.

    Article  Google Scholar 

  11. Yang, L.; Hong, H.; Fu, Q.; Huang, Y. F.; Zhang, J. Y.; Cui, X. D.; Fan, Z. Y.; Liu, K. H.; Xiang, B. Single-crystal atomic-layered molybdenum disulfide nanobelts with high surface activity. ACS Nano 2015, 9, 6478–6483.

    Article  Google Scholar 

  12. 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.

    Article  Google Scholar 

  13. Yu, Z. H.; Pan, Y. M.; Shen, Y. T.; Wang, Z. L.; Ong, Z. Y.; Xu, T.; Xin, R.; Pan, L. J.; Wang, B. G.; Sun, L. T. et al. Towards intrinsic charge transport in monolayer molybdenum disulfide by defect and interface engineering. Nat. Commun. 2014, 5, 5290.

    Article  Google Scholar 

  14. Hong, J. H.; Hu, Z. X.; Probert, M.; Li, K.; Lv, D. H.; Yang, X. N.; Gu, L.; Mao, N. N.; Feng, Q. L.; Xie, L. M. et al. Exploring atomic defects in molybdenum disulphide monolayers. Nat. Commun. 2015, 6, 6293.

    Article  Google Scholar 

  15. Li, H.; Tsai, C.; Koh, A. L.; Cai, L. L.; Contryman, A. W.; Fragapane, A. H.; Zhao, J. H.; Han, H. S.; Manoharan, H. C.; Abild-Pedersen, F. et al. Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. Nat. Mater. 2016, 15, 48–53.

    Article  Google Scholar 

  16. Wang, H. T.; Tsai, C.; Kong, D. S.; Chan, H. 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.

    Article  Google Scholar 

  17. Voiry, D.; Yamaguchi, H.; Li, J. W.; Silva, R.; Alves, D. C. B.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 2013, 12, 850–855.

    Article  Google Scholar 

  18. Yin, Y.; Han, J. C.; Zhang, Y. M.; Zhang, X. H.; Xu, P.; Yuan, Q.; Samad, L.; Wang, X. J.; Wang, Y.; Zhang, Z. H. et al. Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets. J. Am. Chem. Soc. 2016, 138, 7965–7972.

    Article  Google Scholar 

  19. 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.

    Article  Google Scholar 

  20. Geng, X. M.; Jiao, Y. C.; Han, Y.; Mukhopadhyay, A.; Yang, L.; Zhu, H. L. Freestanding metallic 1T MoS2 with dual ion diffusion paths as high rate anode for sodium-ion batteries. Adv. Funct. Mater. 2017, 27, 1702998.

    Article  Google Scholar 

  21. Acerce, M.; Voiry, D.; Chhowalla, M. Metallic 1T phase MoS2 nanosheets as supercapacitor electrode materials. Nat. Nanotechnol. 2015, 10, 313–318.

    Article  Google Scholar 

  22. Lin, Y. C.; Dumcenco, D. O.; Huang, Y. S.; Suenaga, K. Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2. Nat. Nanotechnol. 2014, 9, 391–396.

    Article  Google Scholar 

  23. Kang, Y. M.; Najmaei, S.; Liu, Z.; Bao, Y. J.; Wang, Y. M.; Zhu, X.; Halas, N. J.; Nordlander, P.; Ajayan, P. M.; Lou, J. et al. Plasmonic hot electron induced structural phase transition in a MoS2 monolayer. Adv. Mater. 2014, 26, 6467–6471.

    Article  Google Scholar 

  24. Shi, Y.; Wang, J.; Wang, C.; Zhai, T. T.; Bao, W. J.; Xu, J. J.; Xia, X. H.; Chen, H. Y. Hot electron of Au nanorods activates the electrocatalysis of hydrogen evolution on MoS2 nanosheets. J. Am. Chem. Soc. 2015, 137, 7365–7370.

    Article  Google Scholar 

  25. Sandoval, S. J.; Yang, D.; Frindt, R. F.; Irwin, J. C. Raman study and lattice dynamics of single molecular layers of MoS2. Phys. Rev. B 1991, 44, 3955–3962.

    Article  Google Scholar 

  26. Wang, L. L.; Liu, X.; Luo, J. M.; Duan, X. D.; Crittenden, J.; Liu, C. B.; Zhang, S. Q.; Pei, Y.; Zeng, Y. X.; Duan, X. F. Self-optimization of the active site of molybdenum disulfide by an irreversible phase transition during photocatalytic hydrogen evolution. Angew. Chem., Int. Ed. 2017, 56, 7610–7614.

    Article  Google Scholar 

  27. Geng, X. M.; Sun, W. W.; Wu, W.; Chen, B.; Al-Hilo, A.; Benamara, M.; Zhu, H. L.; Watanabe, F.; Cui, J. B.; Chen, T. P. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction. Nat. Commun. 2016, 7, 10672.

    Article  Google Scholar 

  28. Liu, Q.; Li, X. L.; Xiao, Z. R.; Zhou, Y.; Chen, H. P.; Khalil, A.; Xiang, T.; Xu, J. Q.; Chu, W. S.; Wu, X. J. et al. Stable metallic 1T-WS2 nanoribbons intercalated with ammonia ions: The correlation between structure and electrical/optical properties. Adv. Mater. 2015, 27, 4837–4844.

    Article  Google Scholar 

  29. Wang, D. Z.; Zhang, X. Y.; Bao, S. Y.; Zhang, Z. T.; Fei, H.; Wu, Z. Z. Phase engineering of a multiphasic 1T/2H MoS2 catalyst for highly efficient hydrogen evolution. J. Mater. Chem. A 2017, 5, 2681–2688.

    Article  Google Scholar 

  30. Liu, Q.; Li, X. L.; He, Q.; Khalil, A.; Liu, D. B.; Xiang, T.; Wu, X. J.; Song, L. Gram-scale aqueous synthesis of stable few-layered 1T-MoS2: Applications for visible-light-driven photocatalytic hydrogen evolution. Small 2015, 11, 5556–5564.

    Article  Google Scholar 

  31. Calandra, M. Chemically exfoliated single-layer MoS2: Stability, lattice dynamics, and catalytic adsorption from first principles. Phys. Rev. B 2013, 88, 245428.

    Article  Google Scholar 

  32. Güller, F.; Llois, A. M.; Goniakowski, J.; Noguera, C. Prediction of structural and metal-to-semiconductor phase transitions in nanoscale MoS2, WS2, and other transition metal dichalcogenide zigzag ribbons. Phys. Rev. B 2015, 91, 075407.

    Article  Google Scholar 

  33. Wang, J.; Zhong, H. X.; Wang, Z. L.; Meng, F. L.; Zhang, X. B. Integrated three-dimensional carbon paper/carbon tubes/cobalt-sulfide sheets as an efficient electrode for overall water splitting. ACS Nano 2016, 10, 2342–2348.

    Article  Google Scholar 

  34. Li, D. Q.; Liao Q. Y.; Ren, B. W.; Jin, Q. Y.; Cui, H.; Wang, C. X. A 3D-composite structure of FeP nanorods supported by vertically aligned graphene for the high-performance hydrogen evolution reaction. J. Mater. Chem. A 2017, 5, 11301–11308.

    Article  Google Scholar 

  35. Tang, C.; Zhang, R.; Lu, W. B.; He, L. B.; Jiang, X. E.; Asiri, A. M.; Sun, X. P. Fe-Doped CoP Nanoarray: A monolithic multifunctional catalyst for highly efficient hydrogen generation. Adv. Mater. 2017, 29, 1602441.

    Article  Google Scholar 

  36. Fan, X. B.; Xu, P. T.; Zhou, D. K.; Sun, Y. F.; Li, Y. C.; Nguyen, M. A. T.; Terrones, M.; Mallouk, T. E. Fast and efficient preparation of exfoliated 2H MoS2 nanosheets by sonication-assisted lithium intercalation and infrared laser-induced 1T to 2H phase reversion. Nano. Lett. 2015, 15, 5956–5960.

    Article  Google Scholar 

  37. Cheng, P. F.; Sun. K.; Hu, Y. H. Memristive behavior and ideal memristor of 1T phase MoS2 nanosheets. Nano Lett. 2016, 16, 572–576.

    Article  Google Scholar 

  38. Kappera, R.; Voiry, D.; Yalcin, S. E.; Branch, B.; Gupta, G.; Mohite, A. D.; Chhowalla, M. Phase-engineered low-resistance contacts for ultrathin MoS2 transistors. Nat. Mater. 2014, 13, 1128–1134.

    Article  Google Scholar 

  39. Chou, S. S.; Huang, Y. K.; Kim, J.; Kaehr, B.; Foley, B. M.; Lu, P.; Dykstra, C.; Hopkins, P. E.; Brinker, C. J.; Huang, J. X. et al. Controlling the metal to semiconductor transition of MoS2 and WS2 in solution. J. Am. Chem. Soc. 2015, 137, 1742–1745.

    Article  Google Scholar 

  40. Maitra, U.; Gupta, U.; De, M.; Datta, R.; Govindaraj, A.; Rao, C. N. R. Highly effective visible-light-induced H2 generation by single-layer 1T-MoS2 and a nanocomposite of few-layer 2H-MoS2 with heavily nitrogenated graphene. Angew. Chem., Int. Ed. 2013, 52, 13057–13061.

    Article  Google Scholar 

  41. Ma, L.; Zhou, X. P.; Xu, L. M.; Xu, X. Y.; Zhang, L. L.; Chen, W. X. Chitosan-assisted fabrication of ultrathin MoS2/graphene heterostructures for Li-ion battery with excellent electrochemical performance. Electrochim. Acta 2015, 167, 39–47.

    Article  Google Scholar 

  42. Hu, S.; Wang, X. Single-walled MoO3 nanotubes. J. Am. Chem. Soc. 2008, 130, 8126–8127.

    Article  Google Scholar 

  43. Wang, P. P.; Sun, H. Y.; Ji, Y. J.; Li, W. H.; Wang, X. Three- dimensional assembly of single-layered MoS2. Adv. Mater. 2014, 26, 964–969.

    Article  Google Scholar 

  44. Enyashin, A. N.; Yadgarov, L.; Houben, L.; Popov, I.; Weidenbach, M.; Tenne, R.; Bar-Sadan, M.; Seifert, G. New route for stabilization of 1T-WS2 and MoS2 phases. J. Phys. Chem. C 2011, 115, 24586–24591.

    Article  Google Scholar 

  45. Cai, L.; He, J. F.; Liu, Q. H.; Yao, T.; Chen, L.; Yan, W. S.; Hu, F. C.; Jiang, Y.; Zhao, Y. D.; Hu, T. D. et al. Vacancy-induced ferromagnetism of MoS2 nanosheets. J. Am. Chem. Soc. 2015, 137, 2622–2627.

    Article  Google Scholar 

  46. Hu, S.; Wang. X. Fullerene-like colloidal nanocrystal of nickel hydroxychloride. J. Am. Chem. Soc. 2010, 132, 9573–9575.

    Article  Google Scholar 

  47. Tang, M. L.; Grauer, D. C.; Lassalle-Kaiser, B.; Yachandra, V. K.; Amirav, L.; Long, J. R.; Yano, J.; Alivisatos, A. P. Structural and electronic study of an amorphous MoS3 hydrogen-generation catalyst on a quantum-controlled photosensitizer. Angew. Chem., Int. Ed. 2011, 123, 10385–10389.

    Article  Google Scholar 

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

    Article  Google Scholar 

  49. Li, D. J.; Maiti, U. N.; Lim, J.; Choi, D. S.; Lee, W. J.; Oh, Y.; Lee, G. Y.; Kim, S. O. Molybdenum sulfide/N-doped CNT forest hybrid catalysts for high performance hydrogen evolution reaction. Nano Lett. 2014, 14, 1228–1233.

    Article  Google Scholar 

  50. Wang, H.; Lu, Z.; Xu, S.; Kong, D.; Cha, J. J.; Zheng, G.; Hsu, P.; Yan, K.; Bradshaw, D.; Prinz, F. B. et al. Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction. Proc. Natl. Acad. Sci. USA 2013, 110, 19701–19706.

    Article  Google Scholar 

  51. Tan, S. J. R.; Abdelwahab, I.; Ding, Z. J.; Zhao, X. X.; Yang, T. S.; Loke, G. Z. J.; Lin, H.; Verzhbitskiy, I.; Sock Mui Poh, S. M.; Xu, H. et al. Chemical stabilization of 1T? phase transition metal dichalcogenides with giant optical Kerr nonlinearity. J. Am. Chem. Soc. 2017, 139, 2504–2511.

    Article  Google Scholar 

  52. Cook J. B.; Kim H. S.; Yan Y.; Ko J. S.; Robbennolt S.; Dunn B.; Tolbert S. H. Mesoporous MoS2 as a transition metal dichalcogenide exhibiting pseudocapacitive Li and Na-ion charge storage. Adv. Energy Mater. 2016, 6, 1501937.

    Article  Google Scholar 

  53. Liu, K. K.; Zhang, W. J.; Lee, Y. H.; Lin, Y. C.; Chang, M. T.; Su, C. Y.; Chang, C. S.; Li, H.; Shi, Y. M.; Zhang, H. et al. Growth of large-area and highly crystalline MoS2 thin layers on insulating substrates. Nano Lett. 2012, 12, 1538–1544.

    Article  Google Scholar 

  54. Koroteev, V. O.; Bulusheva, L. G.; Okotrub, A. V.; Yudanov, N. F.; Vyalikh, D. V. Formation of MoS2 nanoparticles on the surface of reduced graphite oxide. Phys. Stat. Solid. B 2011, 248, 2740–2743.

    Article  Google Scholar 

  55. Liao, L.; Zhu, J.; Bian, X. J.; Zhu, L. N.; 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.

    Article  Google Scholar 

  56. 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.

    Article  Google Scholar 

  57. Skúlason, E.; Karlberg, G. S.; Rossmeisl, J.; Bligaard, T.; Greeley, J.; Jónsson, H.; Nørskov, J. K. Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode. Phys. Chem. Chem. Phys. 2007, 9, 3241–3250.

    Article  Google Scholar 

  58. Hinnemann, B.; Moses, P. G.; Bonde, J.; Jørgensen, K. P.; Nielsen, J. H.; Horch, S.; Chorkendorff, I.; Nørskov, J. K. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J. Am. Chem. Soc. 2005, 127, 5308–5309.

    Article  Google Scholar 

  59. Greeley, J.; Nørskov, J. K. Large-scale, density functional theory-based screening of alloys for hydrogen evolution. Surf. Sci. 2007, 601, 1590–1598.

    Article  Google Scholar 

  60. Fan, X. L.; Yang, Y.; Xiao, P.; Lau, W. M. Site-specific catalytic activity in exfoliated MoS2 single-layer polytypes for hydrogen evolution: Basal plane and edges. J. Mater. Chem. A 2014, 2, 20545–20551.

    Article  Google Scholar 

Download references

Acknowledgements

This work has been financially support by the National Natural Science Foundation of China (No. 21676300), the Beijing Natural Science Foundation (No. 2184104), the Fundamental Research Funds for the Central Universities (No. 16CX06007A) and China Postdoctoral Science Foundation (No. 2017M610076).

Author information

Authors and Affiliations

  1. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (East China), 66 WestChangjiang Road, Qingdao, 266580, China

    Kaian Sun, Yunqi Liu, Yuan Pan, Jinchong Zhao, Lingyou Zeng, Zhi Liu & Chenguang Liu

  2. Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Yuan Pan

  3. College of Science, China University of Petroleum (East China), 66 West Changjiang Road, Qingdao, 266580, China

    Houyu Zhu

Authors
  1. Kaian Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yunqi Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yuan Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Houyu Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jinchong Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Lingyou Zeng
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhi Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Chenguang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Yunqi Liu, Yuan Pan or Chenguang Liu.

Electronic supplementary material

12274_2018_2026_MOESM1_ESM.pdf

Targeted bottom-up synthesis of 1T-phase MoS2 arrays with high electrocatalytic hydrogen evolution activityby simultaneous structure and morphology engineering

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sun, K., Liu, Y., Pan, Y. et al. Targeted bottom-up synthesis of 1T-phase MoS2 arrays with high electrocatalytic hydrogen evolution activity by simultaneous structure and morphology engineering. Nano Res. 11, 4368–4379 (2018). https://doi.org/10.1007/s12274-018-2026-8

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-018-2026-8

Keywords

Search

Navigation