Frontiers of Materials Science

, Volume 12, Issue 4, pp 379–391 | Cite as

Electrospun titania fibers by incorporating graphene/Ag hybrids for the improved visible-light photocatalysis

  • Zhongchi Wang
  • Gongsheng Song
  • Jianle Xu
  • Qiang Fu
  • Chunxu PanEmail author
Research Article


A novel graphene/Ag nanoparticles (NPs) hybrid (prepared by a physical method (PM)) was incorporated into electrospun TiO2 fibers to improve visible-lightdriven photocatalytic properties. The experimental study revealed that the graphene/Ag NPs (PM) hybrid not only decreased the bandgap energy of TiO2, but also enhanced its light response in the visible region due to the surface plasmon resonance (SPR) effect. In addition, compared with those of TiO2 fibers incorporating the graphene/Ag NPs hybrid (prepared by a chemical method (CM)), TiO2-graphene/Ag NPs (PM) fibers exhibited a higher surface photocurrent density and superior photocatalytic performance, i.e., the visible-light-driven photocatalytic activity was enhanced by 2 times. The main reasons include a lower surface defect density of the graphene/Ag NPs (PM) hybrid, a smaller particle size (10 nm) and a higher dispersity of Ag NPs, which promote the rapid transfer of photoexcited charge carriers and inhibit the recombination of photogenerated electrons and holes. It is expected that this kind of ternary electrospun fibers will be a promising candidate for applications in water splitting, solar cells, CO2 conversion and optoelectronic devices, etc.


TiO2–graphene/Ag electrospining photocatalysis 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.



This work was supported by the Shenzhen Science and Technology Innovation Committee 2017 basic research (free exploration) project of Shenzhen City of China (No. JCYJ20170303170542173), the National Natural Science Foundation of China (Grant No. 11174227), and the Chinese Universities Scientific Fund.


  1. [1]
    Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode. Nature, 1972, 238(5358): 37–38CrossRefGoogle Scholar
  2. [2]
    Asahi R, Morikawa T, Ohwaki T, et al. Visible-light photocatalysis in nitrogen-doped titanium oxides. Science, 2001, 293(5528): 269–271CrossRefGoogle Scholar
  3. [3]
    Cozzoli P D, Comparelli R, Fanizza E, et al. Photocatalytic activity of organic-capped anatase TiO2 nanocrystals in homogeneous organic solutions. Materials Science and Engineering C, 2003, 23(6–8): 707–713CrossRefGoogle Scholar
  4. [4]
    Chen X, Shen S, Guo L, et al. Semiconductor-based photocatalytic hydrogen generation. Chemical Reviews, 2010, 110(11): 6503–6570CrossRefGoogle Scholar
  5. [5]
    Ni M, Leung M K H, Leung D Y C, et al. A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production. Renewable & Sustainable Energy Reviews, 2007, 11(3): 401–425CrossRefGoogle Scholar
  6. [6]
    O’Regan B, Grätzel M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature, 1991, 353(6346): 737–740CrossRefGoogle Scholar
  7. [7]
    Grätzel M. Photoelectrochemical cells. Nature, 2001, 414(6861): 338–344CrossRefGoogle Scholar
  8. [8]
    Khan S U, Al-Shahry M, Ingler W B Jr. Efficient photochemical water splitting by a chemically modified n-TiO2. Science, 2002, 297(5590): 2243–2245CrossRefGoogle Scholar
  9. [9]
    Lin Z H, Xie Y, Yang Y, et al. Enhanced triboelectric nanogenerators and triboelectric nanosensor using chemically modified TiO2 nanomaterials. ACS Nano, 2013, 7(5): 4554–4560CrossRefGoogle Scholar
  10. [10]
    Chen X, Mao S S. Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. Chemical Reviews, 2007, 107(7): 2891–2959CrossRefGoogle Scholar
  11. [11]
    Ren L, Liu Y D, Qi X, et al. An architectured TiO2 nanosheet with discrete integrated nanocrystalline subunits and its application in lithium batteries. Journal of Materials Chemistry, 2012, 22(40): 21513–21518CrossRefGoogle Scholar
  12. [12]
    Ren L, Qi X, Liu Y D, et al. Upconversion-P25-graphene composite as an advanced sunlight driven photocatalytic hybrid material. Journal of Materials Chemistry, 2012, 22(23): 11765–11771CrossRefGoogle Scholar
  13. [13]
    Tian J, Zhao Z, Kumar A, et al. Recent progress in design, synthesis, and applications of one-dimensional TiO2 nanostructured surface heterostructures: a review. Chemical Society Reviews, 2014, 43(20): 6920–6937CrossRefGoogle Scholar
  14. [14]
    Ge M, Li Q, Cao C, et al. One-dimensional TiO2 nanotube photocatalysts for solar water splitting. Advanced Science, 2017, 4(1): 1600152CrossRefGoogle Scholar
  15. [15]
    Kumar P S, Sundaramurthy J, Sundarrajan S, et al. Hierarchical electrospun nanofibers for energy harvesting, production and environmental remediation. Energy & Environmental Science, 2014, 7(10): 3192–3222CrossRefGoogle Scholar
  16. [16]
    Zhang J, Cai Y B, Hou X B, et al. Preparation of TiO2 nanofibrous membranes with hierarchical porosity for efficient photocatalytic degradation. The Journal of Physical Chemistry C, 2018, 122(16): 8946–8953CrossRefGoogle Scholar
  17. [17]
    Ren L, Li Y Z, Hou J G, et al. The pivotal effect of the interaction between reactant and anatase TiO2 nanosheets with exposed 001 facets on photocatalysis for the photocatalytic purification of VOCs. Applied Catalysis B: Environmental, 2016, 181: 625–634CrossRefGoogle Scholar
  18. [18]
    Wang M, Ioccozia J, Sun L, et al. Inorganic-modified semiconductor TiO2 nanotube arrays for photocatalysis. Energy & Environmental Science, 2014, 7(7): 2182–2202CrossRefGoogle Scholar
  19. [19]
    He Z, Que W, Chen J, et al. Photocatalytic degradation of methyl orange over nitrogen–fluorine codoped TiO2 nanobelts prepared by solvothermal synthesis. ACS Applied Materials & Interfaces, 2012, 4(12): 6816–6826CrossRefGoogle Scholar
  20. [20]
    Lan L, Li Y Z, Zeng M, et al. Efficient UV–vis-infrared lightdriven catalytic abatement of benzene on amorphous manganese oxide supported on anatase TiO2 nanosheet with dominant {001} facets promoted by a photothermocatalytic synergetic effect. Applied Catalysis B: Environmental, 2017, 203: 494–504CrossRefGoogle Scholar
  21. [21]
    Zeng M, Li Y Z, Mao M M, et al. Synergetic effect between photocatalysis on TiO2 and thermocatalysis on CeO2 for gas-phase oxidation of benzene on TiO2/CeO2 nanocomposites. ACS Catalysis, 2015, 5(6): 3278–3286CrossRefGoogle Scholar
  22. [22]
    Liu H H, Li Y Z, Yang Y, et al. Highly efficient UV-vis-infrared catalytic purification of benzene on CeMnxOy/TiO2 nanocomposite, caused by its high thermocatalytic activity and strong absorption in the full solar spectrum region. Journal of Materials Chemistry A, 2016, 4(25): 9890–9899CrossRefGoogle Scholar
  23. [23]
    Ma Y, Li Y Z, Mao M Y, et al. Synergetic effect between photocatalysis on TiO2 and solar light-driven thermocatalysis on MnOx for benzene purification on MnOx/TiO2 nanocomposites. Journal of Materials Chemistry A, 2015, 3(10): 5509–5516CrossRefGoogle Scholar
  24. [24]
    Ren X H, Qi X, Shen Y Z, et al. 2D co-catalytic MoS2 nanosheets embedded with 1D TiO2 nanoparticles for enhancing photocatalytic activity. Journal of Physics D: Applied Physics, 2016, 49(31): 315304–315312CrossRefGoogle Scholar
  25. [25]
    Mohamed A E R, Rohani S. Modified TiO2 nanotube arrays (TNTAs): progressive strategies towards visible light responsive photoanode: a review. Energy & Environmental Science, 2011, 4(4): 1065–1086CrossRefGoogle Scholar
  26. [26]
    Zhang J, Xiao F X, Xiao G, et al. Linker-assisted assembly of 1D TiO2 nanobelts/3D CdS nanospheres hybrid heterostructure as efficient visible light photocatalyst. Applied Catalysis A, 2016, 521: 50–56CrossRefGoogle Scholar
  27. [27]
    Wang C, Astruc D. Nanogold plasmonic photocatalysis for organic synthesis and clean energy conversion. Chemical Society Reviews, 2014, 43(20): 7188–7216CrossRefGoogle Scholar
  28. [28]
    Zhang X Y, Li H P, Cui X L, et al. Graphene/TiO2 nanocomposites: synthesis, characterization and application in hydrogen evolution from water photocatalytic splitting. Journal of Materials Chemistry C, 2010, 20(14): 2801–2806CrossRefGoogle Scholar
  29. [29]
    Kong M, Li Y, Chen X, et al. Tuning the relative concentration ratio of bulk defects to surface defects in TiO2 nanocrystals leads to high photocatalytic efficiency. Journal of the American Chemical Society, 2011, 133(41): 16414–16417CrossRefGoogle Scholar
  30. [30]
    Wen Y, Ding H, Shan Y. Preparation and visible light photocatalytic activity of Ag/TiO2/graphene nanocomposite. Nanoscale, 2011, 3(10): 4411–4417CrossRefGoogle Scholar
  31. [31]
    Zhang Y, Pan C. TiO2/graphene composite from thermal reaction of graphene oxide and its photocatalytic activity in visible light. Journal of Materials Science, 2011, 46(8): 2622–2626CrossRefGoogle Scholar
  32. [32]
    Li X, Zhu J, Wei B. Hybrid nanostructures of metal/twodimensional nanomaterials for plasmon-enhanced applications. Chemical Society Reviews, 2016, 45(11): 3145–3187CrossRefGoogle Scholar
  33. [33]
    Tang X Z, Cao Z, Zhang H B, et al. Growth of silver nanocrystals on graphene by simultaneous reduction of graphene oxide and silver ions with a rapid and efficient one-step approach. Chemical Communications, 2011, 47(11): 3084–3086CrossRefGoogle Scholar
  34. [34]
    Zhou Y, Yang J, He T, et al. Highly stable and dispersive silver nanoparticle–graphene composites by a simple and low-energyconsuming approach and their antimicrobial activity. Small, 2013, 9(20): 3445–3454CrossRefGoogle Scholar
  35. [35]
    Liu C, Wang K, Luo S, et al. Direct electrodeposition of graphene enabling the one-step synthesis of graphene–metal nanocomposite films. Small, 2011, 7(9): 1203–1206CrossRefGoogle Scholar
  36. [36]
    Pavithra C L P, Sarada B V, Rajulapati K V, et al. A new electrochemical approach for the synthesis of copper–graphene nanocomposite foils with high hardness. Scientific Reports, 2014, 4(6): 4049–4055Google Scholar
  37. [37]
    Yang J, Zang C, Sun L, et al. Synthesis of graphene/Ag nanocomposite with good dispersibility and electroconductibility via solvothermal method. Materials Chemistry and Physics, 2011, 129(1–2): 270–274CrossRefGoogle Scholar
  38. [38]
    Guardia L, Villar-Rodil S, Paredes J I, et al. UV light exposure of aqueous graphene oxide suspensions to promote their direct reduction, formation of graphene–metal nanoparticle hybrids and dye degradation. Carbon, 2012, 50(3): 1014–1024CrossRefGoogle Scholar
  39. [39]
    Sygletou M, Tzourmpakis P, Petridis C, et al. Laser induced nucleation of plasmonic nanoparticles on two-dimensional nanosheets for organic photovoltaics. Journal of Materials Chemistry A, 2016, 4(3): 1020–1027CrossRefGoogle Scholar
  40. [40]
    Liu S, Tian J, Wang L, et al. Microwave-assisted rapid synthesis of Ag nanoparticles/graphene nanosheet composites and their application for hydrogen peroxide detection. Journal of Nanoparticle Research, 2011, 13(10): 4539–4548CrossRefGoogle Scholar
  41. [41]
    Zhang Q, Ye S, Chen X, et al. Photocatalytic degradation of ethylene using titanium dioxide nanotube arrays with Ag and reduced graphene oxide irradiated by γ-ray radiolysis. Applied Catalysis B: Environmental, 2017, 203: 673–683CrossRefGoogle Scholar
  42. [42]
    Liu C H, Mao B H, Gao J, et al. Size-controllable self-assembly of metal nanoparticles on carbon nanostructures in room-temperature ionic liquids by simple sputtering deposition. Carbon, 2012, 50(8): 3008–3014CrossRefGoogle Scholar
  43. [43]
    Hummers W S, Offeman R E. Preparation of graphitic oxide. Journal of the American Chemical Society, 1958, 80(6): 1339CrossRefGoogle Scholar
  44. [44]
    Wang C Y, Liu C Y, Liu Y, et al. Surface-enhanced Raman scattering effect for Ag/TiO2 composite particles. Applied Surface Science, 1999, 147(1–4): 52–57CrossRefGoogle Scholar
  45. [45]
    Gao L, Ren W, Li F, et al. Total color difference for rapid and accurate identification of graphene. ACS Nano, 2008, 2(8): 1625–1633CrossRefGoogle Scholar
  46. [46]
    Cançado L G, Jorio A, Ferreira E H, et al. Quantifying defects in graphene via Raman spectroscopy at different excitation energies. Nano Letters, 2011, 11(8): 3190–3196CrossRefGoogle Scholar
  47. [47]
    Zhang L, Zhang Q, Xie H, et al. Electrospun titania nanofibers segregated by graphene oxide for improved visible light photocatalysis. Applied Catalysis B: Environmental, 2017, 201: 470–478CrossRefGoogle Scholar
  48. [48]
    Zhang W F, He Y L, Zhang M S, et al. Raman scattering study on anatase TiO2 nanocrystals. Journal of Physics D: Applied Physics, 2000, 33(8): 912–916CrossRefGoogle Scholar
  49. [49]
    Zhang Y, Li D, Tan X, et al. High quality graphene sheets from graphene oxide by hot-pressing. Carbon, 2013, 54(2): 143–148CrossRefGoogle Scholar
  50. [50]
    Lang Q, Chen Y, Huang T, et al. Graphene “bridge” in transferring hot electrons from plasmonic Ag nanocubes to TiO2 nanosheets for enhanced visible light photocatalytic hydrogen evolution. Applied Catalysis B: Environmental, 2018, 220: 182–190CrossRefGoogle Scholar
  51. [51]
    Zhang J, Xiao F X, Xiao G, et al. Self-assembly of a Ag nanoparticle-modified and graphene-wrapped TiO2 nanobelt ternary heterostructure: surface charge tuning toward efficient photocatalysis. Nanoscale, 2014, 6(19): 11293–11302CrossRefGoogle Scholar
  52. [52]
    Wu J, Luo C, Li D, et al. Preparation of Au nanoparticle-decorated ZnO/NiO heterostructure via nonsolvent method for highperformance photocatalysis. Journal of Materials Science, 2017, 52(3): 1285–1295CrossRefGoogle Scholar
  53. [53]
    Sher ShahMS, Zhang K, Park A R, et al. Single-step solvothermal synthesis of mesoporous Ag–TiO2-reduced graphene oxide ternary composites with enhanced photocatalytic activity. Nanoscale, 2013, 5(11): 5093–5101CrossRefGoogle Scholar
  54. [54]
    Shi J, Chen J, Feng Z, et al. Photoluminescence characteristics of TiO2 and their relationship to the photoassisted reaction of water/methanol mixture. The Journal of Physical Chemistry C, 2007, 111(2): 693–699CrossRefGoogle Scholar
  55. [55]
    Luo C, Li D, Wu W, et al. Preparation of 3D reticulated ZnO/CNF/NiO heteroarchitecture for high-performance photocatalysis. Applied Catalysis B: Environmental, 2015, 166–167: 217–223CrossRefGoogle Scholar
  56. [56]
    Huang H J, Zhen S Y, Li P Y, et al. Confined migration of induced hot electrons in Ag/graphene/TiO2 composite nanorods for plasmonic photocatalytic reaction. Optics Express, 2016, 24(14): 15603–15608CrossRefGoogle Scholar

Copyright information

© Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Zhongchi Wang
    • 1
    • 2
  • Gongsheng Song
    • 1
    • 2
  • Jianle Xu
    • 1
  • Qiang Fu
    • 1
    • 3
  • Chunxu Pan
    • 1
    • 2
    • 3
    Email author
  1. 1.School of Physics and Technology, and MOE Key Laboratory of Artificial Micro- and Nano-structuresWuhan UniversityWuhanChina
  2. 2.Shenzhen Research InstituteWuhan UniversityShenzhenChina
  3. 3.Center for Electron MicroscopyWuhan UniversityWuhanChina

Personalised recommendations