Skip to main content
SpringerLink
Log in

Hydrogenated TiO2/SrTiO3 porous microspheres with tunable band structure for solar-light photocatalytic H2 and O2 evolution

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

The production of H2 and O2 from solar-light photocatalytic water splitting has attracted significant research attention as a clean and renewable source of energy. In this study, hydrogenated TiO2/SrTiO3 porous microspheres were prepared as a high-performance photocatalyst. Titanium glycerolate and then strontium complex precursors were first prepared via a two-step solvothermal process, then, after calcination in air and subsequent H2/Ar reduction treatments, hydrogenated TiO2/SrTiO3 porous microspheres with controllable defects and band positions were prepared. Several characterization techniques were used to demonstrate that the catalyst heterostructures, the oxygen-vacancy content, and the unique porous structures synergistically enhanced the visible-light harvesting abilities and photogenerated charge separation, and resulted in improved photocatalytic efficiency for H2 and O2 evolution. As expected, the optimum treatment conditions provided hydrogenated TiO2/SrTiO3 porous microspheres that showed excellent photocatalytic activity with H2 and O2 evolution rates of 239.97 and 103.79 μmol h−1 (50 mg catalyst, under AM 1.5 irradiation), respectively, which were ca. 5.9 and 6.6 times higher, respectively, than those of solid TiO2/SrTiO3 materials. Thus, this type of hydrogenated TiO2/SrTiO3 porous microsphere catalyst shows great potential as a photocatalyst for solar-energy conversion applications.

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. Xiang Q, Yu J, Jaroniec M. Synergetic effect of MoS2 and graphene as cocatalysts for enhanced photocatalytic H2 production activity of Ti2 nanoparticles. J Am Chem Soc, 2012, 134: 6575–6578

    Article  Google Scholar 

  2. Liu W, Qu Y, Zhou W, et al. A versatile salicylic acid precursor method for preparing titanate microspheres. Sci China Mater, 2015, 58: 106–113

    Article  Google Scholar 

  3. Bi W, Ye C, Xiao C, et al. Spatial location engineering of oxygen vacancies for optimized photocatalytic H2 evolution activity. Small, 2014, 10: 2820–2825

    Article  Google Scholar 

  4. Wang Z, Yang C, Lin T, et al. H-doped black titania with very high solar absorption and excellent photocatalysis enhanced by localized surface plasmon resonance. Adv Funct Mater, 2013, 23: 5444–5450

    Article  Google Scholar 

  5. Srinivasan N, Sakai E, Miyauchi M. Balanced excitation between two semiconductors in bulk heterojunction Z-scheme system for overall water splitting. ACS Catal, 2016, 6: 2197–2200

    Article  Google Scholar 

  6. Li R, Weng Y, Zhou X, et al. Achieving overall water splitting using titanium dioxide-based photocatalysts of different phases. Energy Environ Sci, 2015, 8: 2377–2382

    Article  Google Scholar 

  7. Ouyang S, Tong H, Umezawa N, et al. Surface-alkalinization-induced enhancement of photocatalytic H2 evolution over SrTiO3-based photocatalysts. J Am Chem Soc, 2012, 134: 1974–1977

    Article  Google Scholar 

  8. Niishiro R, Tanaka S, Kudo A. Hydrothermal-synthesized SrTiO3 photocatalyst codoped with rhodium and antimony with visiblelight response for sacrificial H2 and 2 evolution and application to overall water splitting. Appl Catalysis B-Environ, 2014, 150-151: 187–196

    Article  Google Scholar 

  9. Wu QS, Liu JW, Wang GS, et al. A surfactant-free route to synthesize BaxSr1-xTiO3 nanoparticles at room temperature, their dielectric and microwave absorption properties. Sci China Mater, 2016, 59: 609–617

    Article  Google Scholar 

  10. Zhang J, Bang JH, Tang C, et al. Tailored Ti2-SrTiO3 heterostructure nanotube arrays for improved photoelectrochemical performance. ACS Nano, 2010, 4: 387–395

    Article  Google Scholar 

  11. Wang B, Shen S, Guo L. SrTiO3 single crystals enclosed with highindexed {023} facets and {001} facets for photocatalytic hydrogen and oxygen evolution. Appl Catalysis B-Environ, 2015, 166-167: 320–326

    Article  Google Scholar 

  12. Huang JR, Tan X, Yu T, et al. Hetero-structured Ti2/SrTiO3 nanotube array film with highly reactive anatase Ti2 {001} facets. J Mater Chem A, 2014, 2: 9975–9981

    Article  Google Scholar 

  13. Huang BS, Su EC, Wey MY. Design of a Pt/Ti2–xNx/SrTiO3 triplejunction for effective photocatalytic H2 production under solar light irradiation. Chem Eng J, 2013, 223: 854–859

    Article  Google Scholar 

  14. Maeda K. Z-scheme water splitting using two different semiconductor photocatalysts. ACS Catal, 2013, 3: 1486–1503

    Article  Google Scholar 

  15. Lan ZA, Zhang G, Wang X. A facile synthesis of Br-modified g-C3N4 semiconductors for photoredox water splitting. Appl Catalysis B-Environ, 2016, 192: 116–125

    Article  Google Scholar 

  16. Jiao Z, Zhang Y, Chen T, et al. Ti2 nanotube arraysmodified with Cr-doped SrTiO3 nanocubes for highly efficient hydrogen evolution under visible light. Chem Eur J, 2014, 20: 2654–2662

    Article  Google Scholar 

  17. Zhao W, Li Y, Zhang M, et al. Direct microwave–hydrothermal synthesis of Fe-doped titania with extended visible-light response and enhancedH2-production performance. Chem Eng J, 2016, 283: 105–113

    Article  Google Scholar 

  18. Hoang S, Berglund SP, Hahn NT, et al. Enhancing visible light photo-oxidation of water with Ti2 nanowire arrays via cotreatment with H2and NH3: synergistic effects between Ti3+ and N. J Am Chem Soc, 2012, 134: 3659–3662

    Article  Google Scholar 

  19. Lin T, Yang C, Wang Z, et al. Effective nonmetal incorporation in black titania with enhanced solar energy utilization. Energy Environ Sci, 2014, 7: 967–972

    Article  Google Scholar 

  20. Lian Z, Xu P, Wang W, et al. C60-decorated CdS/Ti2 mesoporous architectures with enhanced photostability and photocatalytic activity for H2 evolution. ACS Appl Mater Interfaces, 2015, 7: 4533–4540

    Article  Google Scholar 

  21. Chang K, Mei Z, Wang T, et al. MoS2/graphene cocatalyst for efficient photocatalytic H2 evolution under visible light irradiation. ACS Nano, 2014, 8: 7078–7087

    Article  Google Scholar 

  22. Chen X, Liu L, Yu PY, et al. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science, 2011, 331: 746–750

    Article  Google Scholar 

  23. Xiao Y, Chen Y, Xie Y, et al. Hydrogenated Ce2-xSx mesoporous hollow spheres for enhanced solar driven water oxidation. Chem Commun, 2016, 52: 2521–2524

    Article  Google Scholar 

  24. Tan H, Zhao Z, Zhu W, et al. Oxygen vacancy enhanced photocatalytic activity of pervoskite SrTiO3. ACS Appl Mater Interfaces, 2014, 6: 19184–19190

    Article  Google Scholar 

  25. Yu X, Kim B, Kim YK. Highly enhanced photoactivity of anatase Ti2 nanocrystals by controlled hydrogenation-induced surface defects. ACS Catal, 2013, 3: 2479–2486

    Article  Google Scholar 

  26. Chen X, Liu L, Huang F. Black titanium dioxide (Ti2) nanomaterials. Chem Soc Rev, 2015, 44: 1861–1885

    Article  Google Scholar 

  27. Zhou W, Li W, Wang JQ, et al. Ordered mesoporous black Ti2 as highly efficient hydrogen evolution photocatalyst. JAmChem Soc, 2014, 136: 9280–9283

    Article  Google Scholar 

  28. Zhao H, Wu M, Liu J, et al. Synergistic promotion of solar-driven H2 generation by three-dimensionally orderedmacroporous structured Ti2-Au-CdS ternary photocatalyst. Appl Catalysis B-Environ, 2016, 184: 182–190

    Article  Google Scholar 

  29. Li K, Chai B, Peng T, et al. Preparation of AgIn5S8/Ti2 heterojunction nanocomposite and its enhanced photocatalytic H2 production property under visible light. ACS Catal, 2013, 3: 170–177

    Article  Google Scholar 

  30. Wang Z, Wu L, Chen M, et al. Facile synthesis of superparamagnetic fluorescent Fe3O4/ZnS hollow nanospheres. J Am Chem Soc, 2009, 131: 11276–11277

    Article  Google Scholar 

  31. Zhang Y, Wu B, Tang Y, et al. Prolonged electron lifetime in ordered Ti2mesophyll cell-likemicrospheres for efficient photocatalytic water reduction and oxidation. Small, 2016, 12: 2291–2299

    Article  Google Scholar 

  32. Bai H, Juay J, Liu Z, et al. Hierarchical SrTiO3/Ti2 nanofibers heterostructures with high efficiency in photocatalytic H2 generation. Appl Catalysis B-Environ, 2012, 125: 367–374

    Article  Google Scholar 

  33. Ng J, Xu S, Zhang X, et al. Hybridized nanowires and cubes: a novel architecture of a heterojunctioned Ti2/SrTiO3 thin film for efficient water splitting. Adv Funct Mater, 2010, 20: 4287–4294

    Article  Google Scholar 

  34. Wu Z, Su Y, Yu J, et al. Enhanced photoelectrocatalytic hydrogen production activity of SrTiO3–Ti2 hetero-nanoparticle modified Ti2 nanotube arrays. Int JHydrogen Energy, 2015, 40: 9704–9712

    Article  Google Scholar 

  35. Tian G, Chen Y, Zhou W, et al. 3D hierarchical flower-like Ti2 nanostructure: morphology control and its photocatalytic property. CrystEngComm, 2011, 13: 2994–3000

    Article  Google Scholar 

  36. Ran J, Ma TY, Gao G, et al. Porous P-doped graphitic carbon nitride nanosheets for synergistically enhanced visible-light photocatalytic H2 production. Energy Environ Sci, 2015, 8: 3708–3717

    Article  Google Scholar 

  37. Zhang M, Luo Z, Zhou M, et al. Photocatalytic water oxidation by layered Co/h-BCN hybrids. Sci China Mater, 2015, 58: 867–876

    Article  Google Scholar 

  38. Paier J, Penschke C, Sauer J. Oxygen defects and surface chemistry of ceria: quantum chemical studies compared to experiment. Chem Rev, 2013, 113: 3949–3985

    Article  Google Scholar 

  39. Bai X, Wang L, Zhu Y. Visible photocatalytic activity enhance-ment of ZnWO4 by graphene hybridization. ACS Catal, 2012, 2: 2769–2778

    Article  Google Scholar 

  40. Li H, Chen J, Xia Z, et al. Microwave-assisted preparation of selfdoped Ti2 nanotube arrays for enhanced photoelectrochemical water splitting. J Mater Chem A, 2015, 3: 699–705

    Article  Google Scholar 

  41. Yan J, Wang T, Wu G, et al. Tungsten oxide single crystal nanosheets for enhancedmultichannel solar light harvesting. AdvMater, 2015, 27: 1580–1586

    Google Scholar 

  42. Guo S, Zhao T, Jin Z, et al. Self-assembly synthesis of preciousmetal-free 3D ZnO nano/micro spheres with excellent photocatalytic hydrogen production from solar water splitting. J Power Sources, 2015, 293: 17–22

    Article  Google Scholar 

  43. Zhang X, Peng T, Yu L, et al. Visible/near-infrared-light-induced H2 production over g-C3N4 co-sensitized by organic dye and zinc phthalocyanine derivative. ACS Catal, 2015, 5: 504–510

    Article  Google Scholar 

  44. Hara S, Yoshimizu M, Tanigawa S, et al. Hydrogen and oxygen evolution photocatalysts synthesized from strontium titanate by controlled doping and their performance in two-step overall water splitting under visible light. J Phys Chem C, 2012, 116: 17458–17463

    Article  Google Scholar 

  45. Zhang X, Yu L, Zhuang C, et al. Highly asymmetric phthalocyanine as a sensitizer of graphitic carbon nitride for extremely efficient photocatalytic H2 production under near-infrared light. ACS Catal, 2014, 4: 162–170

    Article  Google Scholar 

  46. Luo Z, Poyraz AS, Kuo CH, et al. Crystalline mixed phase (anatase/rutile) mesoporous titanium dioxides for visible light photocatalytic activity. Chem Mater, 2015, 27: 6–17

    Article  Google Scholar 

  47. Ran J, Zhang J, Yu J, et al. Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting. Chem Soc Rev, 2014, 43: 7787–7812

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (51272070, 21631004, 21371053, and 21376065), the Project for Foshan Innovation Group (2014IT100062), the Application Technology Research and Development Projects in Harbin (2013AE4BW051), the International Science & Technology Cooperation Program of China (2014DFR41110), the Natural Science Foundation of Heilongjiang province (E201455), the Postdoctoral Science-research Developmental Foundation of Heilongjiang province (LBH-Q13136), and the Special Fund of Technological Innovation Talents in Harbin City (2015RAQXJ003).

Author information

Authors and Affiliations

  1. Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of China, Heilongjiang University, Harbin, 150080, China

    Taoran Han, Yajie Chen, Guohui Tian, Wei Zhou, Yuting Xiao, Jinxin Li & Honggang Fu

  2. National Center for International Research on Catalytic technology, Harbin, 150080, China

    Guohui Tian & Honggang Fu

Authors
  1. Taoran Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yajie Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Guohui Tian
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Wei Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yuting Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jinxin Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Honggang Fu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Guohui Tian or Honggang Fu.

Additional information

Taoran Han received her MSc degree from Heilongjiang University under the supervision of Prof. Guohui Tian. Her research interests include the photocatalytic water splitting, photoelectrochemistry water splitting and controlled synthesis of nanomaterials.

Honggang Fu received his BSc and MSc degrees from Jilin University in 1984 and 1987, respectively. Then, he joined Heilongjiang University as an assistant professor. In 1999, he received his PhD degree fromHarbin Institute of Technology. He became a full professor in 2000. Currently, he is a Cheung Kong Scholar Professor. His interests focus on oxide-based semiconductor nanomaterials for solar energy conversion and photocatalysis, and crystalline carbon-based nanomaterials for energy conversion and storage. Up to now, he has published more than 260 peer-reviewed papers with over 4500 citations.

Electronic supplementary material

40843_2016_5126_MOESM1_ESM.pdf

Hydrogenated TiO2/SrTiO3 porous microspheres with tunable band structure for solar-light photocatalytic H2 and O2 evolution

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Han, T., Chen, Y., Tian, G. et al. Hydrogenated TiO2/SrTiO3 porous microspheres with tunable band structure for solar-light photocatalytic H2 and O2 evolution. Sci. China Mater. 59, 1003–1016 (2016). https://doi.org/10.1007/s40843-016-5126-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-016-5126-1

Keywords

Search

Navigation