Journal of Materials Science

, Volume 49, Issue 4, pp 1854–1860 | Cite as

Preparation of ZnO/graphene heterojunction via high temperature and its photocatalytic property

  • Delong Li
  • Wenhui Wu
  • Yupeng Zhang
  • Liangliang Liu
  • Chunxu Pan


This paper introduces a novel electrochemical route for preparing the ZnO/graphene heterojunction composite via high temperature. This process includes: (1) depositing the electrochemically reduced graphene oxide (ERGO) on ITO glass via cyclic voltammetry; (2) pulse plating a zinc (Zn) layer on the ERGO; (3) thermally treating the Zn/ERGO composite and “in situ” to obtain the ZnO/ERGO composite. SEM characterizations revealed that the Zinc Oxide (ZnO) particles were homogenously distributed on the surface of graphene sheets. XRD and Raman spectra found a ZnCO3 phase in the ZnO/ERGO composite, which demonstrated that when the Zn film transformed into ZnO particles during thermal treatment, Zn also reacted with graphene and formed a ZnCO3 intermediate layer at the interface between ZnO and ERGO via short-range diffusion. Compared with the heterojunction formed from regular chemical route, the present process provided a tight contact and combination between ZnO and ERGO, which eventually led to a heterojunction between ZnO and graphene sheets. This heterojunction exhibited great improvement for separation efficiency of photo-generate electron–hole pairs. Experimental results of ultraviolet–visible (UV–Vis) light catalysis demonstrated that the photocatalytic activity of the ZnO/ERGO composite had been greatly improved, and exhibited a value of three times higher than that of pure ZnO.


Graphene Oxide Photocatalytic Activity Graphene Sheet Photocatalytic Property Terephthalic Acid 



This research was supported by the National Natural Science Foundation of China (Nos. 11174227, 51209023, J1210061), and the Fundamental Research Funds for the Central Universities.


  1. 1.
    Zhang JT, Xiong ZG, Zhao XS (2011) Graphene-metal-oxide composites for the degradation of dyes under visible light irradiation. J Mater Chem 21:3634CrossRefGoogle Scholar
  2. 2.
    Zhang YP, Cao B, Zhang B, Qi X, Pan CX (2012) The production of nitrogen-doped graphene from mixed amine plus ethanol flames. Thin Solid Films 520:6850CrossRefADSGoogle Scholar
  3. 3.
    Park WI, Lee CH, Lee JM, Kim NJ, Yi GC (2011) Inorganic nanostructures grown on graphene layers. Nanoscale 3:3522PubMedCrossRefADSGoogle Scholar
  4. 4.
    Zhang YP, Pan CX (2011) TiO2/graphene composite from thermal reaction of graphene oxide and its photocatalytic activity in visible light. J Mater Sci 46:2622MathSciNetCrossRefADSGoogle Scholar
  5. 5.
    Williams G, Kamat PV (2009) Graphene-semiconductor nanocomposites: excited-state interactions between ZnO nanoparticles and graphene oxide. Langmuir 25:13869PubMedCrossRefGoogle Scholar
  6. 6.
    Zhang YP, Li CZ, Pan CX (2012) N + Ni Co doped anatase TiO2 nanocrystals with exposed {001} facets through two-step hydrothermal route. J Am Ceram Soc 95:2951CrossRefGoogle Scholar
  7. 7.
    Zhang YP, Fei LF, Jiang XD, Pan CX, Wang Y (2011) Engineering nanostructured Bi2WO6-TiO2 toward effective utilization of natural light in photocatalysis. J Am Ceram Soc 94:4157CrossRefGoogle Scholar
  8. 8.
    Li DL, Pan CX (2012) Fabrication and characterization of electrospun TiO2/CuS micro-nano-scaled composite fibers. Prog Nat Sci 22:59CrossRefGoogle Scholar
  9. 9.
    Li DL, Jiang XD, Zhang YP, Zhang B, Pan CX (2013) A novel route to ZnO/TiO2 heterojunction composite fibers. J Mater Res 28:507CrossRefADSGoogle Scholar
  10. 10.
    Djurisic AB, Chen XY, Leung YH, Ng A (2012) ZnO nanostructures: growth, properties and applications. J Mater Chem 22:6526CrossRefGoogle Scholar
  11. 11.
    Kim YJ, Lee JH, Yi GC (2009) Vertically aligned ZnO nanostructures grown on graphene layers. Appl Phys Lett 95:213101CrossRefADSGoogle Scholar
  12. 12.
    Hwang JO, Lee DH, Kim JY, Han TH, Kim BH, Park M, No K, Kim SO (2011) Vertical ZnO nanowires/graphene hybrids for transparent and flexible field emission. J Mater Chem 21:3432CrossRefGoogle Scholar
  13. 13.
    Lin J, Penchev M, Wang GP, Paul RK, Zhong JB, Jing XY, Ozkan M, Ozkan CS (2010) Heterogeneous graphene nanostructures: ZnO nanostructures grown on large-area graphene layers. Small 6:2448PubMedCrossRefGoogle Scholar
  14. 14.
    Lu T, Pan LK, Li HB, Zhu G, Lv T, Liu XJ, Sun Z, Chen T, Chua DHC (2011) Microwave-assisted synthesis of graphene-ZnO nanocomposite for electrochemical supercapacitors. J Alloy Compd 509:5488CrossRefGoogle Scholar
  15. 15.
    Zhang YP, Li HB, Pan LK, Lu T, Sun Z (2009) Capacitive behavior of graphene-ZnO composite film for supercapacitors. J Electroanal Chem 634:68CrossRefGoogle Scholar
  16. 16.
    Zheng WT, Ho YM, Tian HW, Wen M, Qi JL, Li YA, Li YA (2009) Field emission from a composite of graphene sheets and ZnO nanowires. J Phys Chem C 113:9164CrossRefGoogle Scholar
  17. 17.
    Yin ZY, Wu SX, Zhou XZ, Huang X, Zhang Q, Boey F, Zhang H (2010) Electrochemical deposition of ZnO nanorods on transparent reduced graphene oxide electrodes for hybrid solar cells. Small 6:307PubMedCrossRefGoogle Scholar
  18. 18.
    Li BJ, Cao HQ (2011) ZnO@graphene composite with enhanced performance for the removal of dye from water. J Mater Chem 21:3346CrossRefGoogle Scholar
  19. 19.
    Xu TG, Zhang LW, Cheng HY, Zhu YF (2011) Significantly enhanced photocatalytic performance of ZnO via graphene hybridization and the mechanism study. Appl Catal B-Environ 101:382CrossRefGoogle Scholar
  20. 20.
    Guo HL, Wang XF, Qian QY, Wang FB, Xia XH (2009) A green approach to the synthesis of graphene nanosheets. ACS Nano 3:2653PubMedCrossRefGoogle Scholar
  21. 21.
    Yu W, Pan CX (2009) Low temperature thermal oxidation synthesis of ZnO nanoneedles and the growth mechanism. Mater Chem Phys 115:74CrossRefGoogle Scholar
  22. 22.
    Kovtyukhova NI, Ollivier PJ, Martin BR, Mallouk TE, Chizhik SA, Buzaneva EV, Gorchinskiy AD (1999) Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations. Chem Mater 11:771CrossRefGoogle Scholar
  23. 23.
    Hirakawa T, Nosaka Y (2002) Properties of O2•- and OH• formed in TiO2 aqueous suspensions by photocatalytic reaction and the influence of H2O2 and some ions. Langmuir 18:3247CrossRefGoogle Scholar
  24. 24.
    Jiang XD, Shi AQ, Wang YQ, Li YZ, Pan CX (2011) Effect of surface microstructure of TiO2 film from micro-arc oxidation on its photocatalytic activity: a HRTEM study. Nanoscale 3:3573PubMedCrossRefADSGoogle Scholar
  25. 25.
    Kashif M, Ali S, Ali ME, Abdulgafour HI, Hashim H, Willander M, Hassan Z (2012) Morphological, optical, and raman characteristics of ZnO nanoflakes prepared via a sol-gel method. Phys Status Solidi A 209:143CrossRefADSGoogle Scholar
  26. 26.
    Brandes EA, Brook GB (1992) Smithells metals reference book, vol 13, 7th edn. Butterworth-Heinemann, OxfordGoogle Scholar
  27. 27.
    Ren ZS, Hu XJ, Xue XX, Chou KC (2013) Solid state reaction studies in Fe3O4–TiO2 system by diffusion couple method. J Alloy Comp 580:182CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  • Delong Li
    • 1
  • Wenhui Wu
    • 1
  • Yupeng Zhang
    • 1
  • Liangliang Liu
    • 1
  • Chunxu Pan
    • 1
    • 2
    • 3
  1. 1.School of Physics and Technology, and MOE Key Laboratory of Artificial Micro- and Nano-structuresWuhan UniversityWuhanChina
  2. 2.Center for Electron MicroscopyWuhan UniversityWuhanChina
  3. 3.Department of Materials Physics, School of Physics and TechnologyWuhan UniversityWuhanChina

Personalised recommendations