Journal of Materials Science

, Volume 53, Issue 14, pp 10338–10350 | Cite as

Composite structures for enhanced photoelectrochemical activity: WS2 quantum dots with oriented WO3 arrays

  • Yong-Hao Xiao
  • Yu-Xiang Yu
  • Wei-De Zhang
Energy materials


Novel visible-light-driven WO3 nanorod arrays with oriented (200) facet were successfully synthesized via a facile solvothermal process using mixed ethanol and water as solvents. Subsequently, WS2 quantum dots (QDs) derived from bulk WS2 powder via ultrasonication were interspersed on WO3 nanorod arrays. The presence of suitable volume ratio of ethanol is a key factor to achieve greater exposure of the WO3 (200) facet. The morphologies, microstructures and optical properties of the prepared samples were systematically explored. The results illustrated that the preferential exposure on the (200) facet of WO3 nanorods as well as the efficient relative electrochemically active surface areas provided by WS2 QDs could facilitate the charge transfer between WS2 QDs and the (200) facet of WO3 nanorods. This study provides a promising approach to design high performance photoanodes for photoelectrochemical water splitting.



This work was financially supported by National Natural Science Foundation of China (21773074) and Guangdong Natural Science Foundation (2014A030311039).

Supplementary material

10853_2018_2303_MOESM1_ESM.pdf (2.9 mb)
Supplementary material 1 (PDF 2930 kb)


  1. 1.
    Wang Q, Hisatomi T, Jia QX, Tokudome H, Zhong M, Wang CZ et al (2016) Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1%. Nat Mater 15:611–615CrossRefGoogle Scholar
  2. 2.
    Zhang J, Ma HP, Liu ZF (2017) Highly efficient photocatalyst based on all oxides WO3/Cu2O heterojunction for photoelectrochemical water splitting. Appl Catal B Environ 201:84–91CrossRefGoogle Scholar
  3. 3.
    Wen W, Yao JC, Gu YJ, Sun TL, Tian H, Zhou QL et al (2017) Balsam-pear-like rutile/anatase core/shell titania nanorod arrays for photoelectrochemical water splitting. Nanotechnology 28:465602–465610CrossRefGoogle Scholar
  4. 4.
    Liu Y, Su FY, Yu YX, Zhang WD (2016) Nano g-C3N4 modified Ti-Fe2O3 vertically arrays for efficient photoelectrochemical generation of hydrogen under visible light. Int J Hydrog Eng 41:7270–7279CrossRefGoogle Scholar
  5. 5.
    Prevot MS, Sivula K (2013) Photoelectrochemical tandem cells for solar water splitting. J Phys Chem C 117:17879–17893CrossRefGoogle Scholar
  6. 6.
    Hilliard S, Baldinozzi G, Friedrich D, Kressman S, Strub H, Artero V et al (2017) Mesoporous thin film WO3 photoanode for photoelectrochemical water splitting: a sol–gel dip coating approach. Sustain Ener Fuel 1:145–153CrossRefGoogle Scholar
  7. 7.
    Ho GW, Chua KJ, Siow DR (2012) Metal loaded WO3 particles for comparative studies of photocatalysis and electrolysis solar hydrogen production. Chem Eng J 181:661–666CrossRefGoogle Scholar
  8. 8.
    Hu DY, Diao P, Xu D, Wu QY (2016) Gold/WO3 nanocomposite photoanodes for plasmonic solar water splitting. Nano Res 9:1735–1751CrossRefGoogle Scholar
  9. 9.
    Zheng F, Man WK, Guo M, Zhang M, Zhen Q (2015) Effects of morphology, size and crystallinity on the electrochromic properties of nanostructured WO3 films. CrystEngComm 17:5440–5450CrossRefGoogle Scholar
  10. 10.
    Fernandez-Dornene RM, Sanchez-Tovar R, Segura-Sanchis E, Garcia-Anton J (2016) Novel tree-like WO3 nanoplatelets with very high surface area synthesized by anodization under controlled hydrodynamic conditions. Chem Eng J 286:59–67CrossRefGoogle Scholar
  11. 11.
    Xiao YH, Xu CQ, Zhang WD (2017) Facile synthesis of Ni-doped WO3 nanoplate arrays for effective photoelectrochemical water splitting. J Solid State Electrochem 21:3355–3364CrossRefGoogle Scholar
  12. 12.
    Kalanur SS, Yoo IH, Seo H (2017) Fundamental investigation of Ti doped WO3 photoanode and their influence on photoelectrochemical water splitting activity. Electrochim Acta 254:348–357CrossRefGoogle Scholar
  13. 13.
    Xiao YH, Zhang WD (2017) MoS2 quantum dots interspersed WO3 nanoplatelet arrays with enhanced photoelectrochemical activity. Electrochim Acta 252:416–423CrossRefGoogle Scholar
  14. 14.
    Ding J, Zhang L, Liu QQ, Dai WL, Guan GF (2017) Synergistic effects of electronic structure of WO3 nanorods with the dominant 001 exposed facets combined with silver size-dependent on the visible-light photocatalytic activity. Appl Catal B Environ 203:335–342CrossRefGoogle Scholar
  15. 15.
    Zhan FQ, Liu WH, Li WZ, Li J, Yang YH, Liu Q et al (2017) Boric acid assisted synthesis of WO3 nanostructures with highly reactive (002) facet and enhanced photoelectrocatalytic activity. J Mater Sci Mater 28:13836–13845CrossRefGoogle Scholar
  16. 16.
    Wang SC, Chen HJ, Gao GP, Butburee T, Lyu MQ, Thaweesak S et al (2016) Synergistic crystal facet engineering and structural control of WO3 films exhibiting unprecedented photoelectrochemical performance. Nano Energy 24:94–102CrossRefGoogle Scholar
  17. 17.
    Zheng JY, Song G, Hong JS, Van TK, Pawar AU, Kim DY et al (2014) Facile fabrication of WO3 nanoplates thin films with dominant crystal facet of (002) for water splitting. Cryst Growth Des 14:6057–6066CrossRefGoogle Scholar
  18. 18.
    Zhang JJ, Zhang P, Wang T, Gong JL (2015) Monoclinic WO3 nanomultilayers with preferentially exposed (002) facets for photoelectrochemical water splitting. Nano Energy 11:189–195CrossRefGoogle Scholar
  19. 19.
    Ghorai A, Bayan S, Gogurla N, Midya A, Ray SK (2017) Highly luminescent WS2 quantum dots/ZnO heterojunctions for light emitting devices. Acs Appl Mater Inter 9:558–565CrossRefGoogle Scholar
  20. 20.
    Liu ZF, Wu JY, Zhang L (2016) Quantum dots and plasmonic Ag decorated WO3 nanorod photoanodes with enhanced photoelectrochemical performances. Int J Hydrog Energy 41:20529–20535CrossRefGoogle Scholar
  21. 21.
    Tubtimtae A, Cheng KY, Lee MW (2014) Ag2S quantum dot-sensitized WO3 photoelectrodes for solar cells. J Solid State Electrochem 18:1627–1633CrossRefGoogle Scholar
  22. 22.
    Kim MJ, Jeon SJ, Kang TW, Ju JM, Yim D, Kim HI et al (2017) 2H-WS2 Quantum dots produced by modulating the dimension and phase of 1T-nanosheets for antibody-free optical sensing of neurotransmitters. Acs Appl Mater Inter 9:12316–12323CrossRefGoogle Scholar
  23. 23.
    Zhou LY, Yan SC, Wu H, Song HZ, Shi Y (2017) Facile sonication synthesis of WS2 quantum dots for photoelectrochemical performance. Catalysts 7:18–26CrossRefGoogle Scholar
  24. 24.
    Ahn SH, Manthiram A (2016) Edge-oriented tungsten disulfide catalyst produced from mesoporous WO3 for highly efficient dye-sensitized solar cells. Adv Energy Mater 6:1501814–1501820CrossRefGoogle Scholar
  25. 25.
    Xu SJ, Li D, Wu PY (2015) One-pot, facile, and versatile synthesis of monolayer MoS2/WS2 quantum dots as bioimaging probes and efficient electrocatalysts for hydrogen evolution reaction. Adv Funct Mater 25:1127–1136CrossRefGoogle Scholar
  26. 26.
    Valappil MO, Anil A, Shaijumon M, Pillai VK, Alwarappan S (2017) A single-step electrochemical synthesis of luminescent WS2 quantum dots. Chem Eur J 23:9144–9148CrossRefGoogle Scholar
  27. 27.
    Long H, Tao LL, Chiu CP, Tang CY, Fung KH, Chai Y et al (2016) The WS2 quantum dot: preparation, characterization and its optical limiting effect in polymethylmethacrylate. Nanotechnology 27:414005–414011CrossRefGoogle Scholar
  28. 28.
    Zeng QY, Li JH, Bai J, Li XJ, Xia LG, Zhou BX (2017) Preparation of vertically aligned WO3 nanoplate array films based on peroxotungstate reduction reaction and their excellent photoelectrocatalytic performance. Appl Catal B Environ 202:388–396CrossRefGoogle Scholar
  29. 29.
    Zhang WY, Zhao JG, Liu ZZ, Liu ZJ, Fu ZX (2010) Influence of growth temperature of TiO2 buffer on structure and PL properties of ZnO films. Appl Surf Sci 256:4423–4425CrossRefGoogle Scholar
  30. 30.
    Xiao YH, Pan ZC, Tian XL, Zhang HC, Zeng XF, Xiao CM et al (2014) Time controlled synthesis of urchin-like zinc oxide and characterization of its optical properties. Mater Lett 131:94–96CrossRefGoogle Scholar
  31. 31.
    Upadhyay SB, Mishra RK, Sahay PP (2016) Cr-doped WO3 nanosheets: structural, optical and formaldehyde sensing properties. Ceram Int 42:15301–15310CrossRefGoogle Scholar
  32. 32.
    Wang YR, Liu B, Xiao SH, Wang XH, Sun LM, Li H et al (2016) Low-temperature H2S detection with hierarchical Cr-doped WO3 microspheres. Acs Appl Mater Inter 8:9674–9683CrossRefGoogle Scholar
  33. 33.
    Li Y, Wang C, Zheng H, Wan F, Yu F, Zhang X et al (2017) Surface oxygen vacancies on WO3 contributed to enhanced photothermo-synergistic effect. Appl Surf Sci 391:654–661CrossRefGoogle Scholar
  34. 34.
    Xu YF, Rao HS, Chen BX, Lin Y, Chen HY, Kuang DB et al (2015) Achieving highly efficient photoelectrochemical water oxidation with a TiCl4 treated 3D antimony-doped SnO2 macropore/branched alpha-Fe2O3 nanorod heterojunction photoanode. Adv Sci 2:150049–150057Google Scholar
  35. 35.
    Lee MG, Kim DH, Sohn W, Moon CW, Park H, Lee S et al (2016) Conformally coated BiVO4 nanodots on porosity-controlled WO3 nanorods as highly efficient type II heterojunction photoanodes for water oxidation. Nano Energy 28:250–260CrossRefGoogle Scholar
  36. 36.
    Yang L, Xiong YL, Guo WL, Guo JN, Gao D, Zhang YH et al (2017) Mo6+ doped BiVO4 with improved charge separation and oxidation kinetics for photoelectrochemical water splitting. Electrochim Acta 256:268–277CrossRefGoogle Scholar
  37. 37.
    Hong SJ, Lee S, Jang JS, Lee JS (2011) Heterojunction BiVO4/WO3 electrodes for enhanced photoactivity of water oxidation. Energy Environ Sci 4:1781–1787CrossRefGoogle Scholar
  38. 38.
    Gao EP, Wang WZ, Shang M, Xu JH (2011) Synthesis and enhanced photocatalytic performance of graphene-Bi2WO6 composite. Phys Chem Chem Phys 13:2887–2893CrossRefGoogle Scholar
  39. 39.
    Wei YJ, Chang XX, Wang T, Li CC, Gong JL (2017) A low-cost NiO hole transfer layer for ohmic back contact to Cu2O for photoelectrochemical water splitting. Small 13:1702007–1702013CrossRefGoogle Scholar
  40. 40.
    Wang H, Qiu XQ, Liu WF, Yang DJ (2017) Facile preparation of well-combined lignin-based carbon/ZnO hybrid composite with excellent photocatalytic activity. Appl Surf Sci 426:206–216CrossRefGoogle Scholar
  41. 41.
    Zhu ZF, Yan Y, Li JQ (2016) One-step synthesis of flower-like WO3/Bi2WO6 heterojunction with enhanced visible light photocatalytic activity. J Mater Sci 51:2112–2120. CrossRefGoogle Scholar
  42. 42.
    McCrory CCL, Jung S, Ferrer IM, Chatman SM, Peters JC, Jaramillo TF (2015) Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. J Am Chem Soc 137:4347–4357CrossRefGoogle Scholar
  43. 43.
    Feng XY, Chen YB, Qin ZX, Wang ML, Guo LJ (2016) Facile fabrication of sandwich structured WO3 nanoplate arrays for efficient photoelectrochemical water splitting. Acs Appl Mater Inter 8:18089–18096CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Chemistry and Chemical EngineeringSouth China University of TechnologyGuangzhouPeople’s Republic of China

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