Environmental Science and Pollution Research

, Volume 24, Issue 13, pp 12416–12425 | Cite as

Synthesis and photocatalytic performance of reduced graphene oxide–TiO2 nanocomposites for orange II degradation under UV light irradiation

  • Tengfei Li
  • Tiecheng Wang
  • Guangzhou QuEmail author
  • Dongli Liang
  • Shibin Hu
Research Article


To enhance the photocatalytic activity of TiO2, reduced graphene oxide–TiO2 (RGO–TiO2) composites with sandwich-like structure were synthesized using a simple solvothermal method. The morphology, crystalline information, and structural property of the photocatalyst were characterized by field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Fourier transmission infrared spectroscopy. The photocatalytic performances of the RGO–TiO2 composites were evaluated by the degradation of orange II (AO7) in water under UV light irradiation. The results showed that the RGO–TiO2 composites exhibited much higher photocatalytic activity than TiO2 and that the removal efficiency of AO7 could reach above 95% only after 20 min of UV light irradiation under the optimum condition. The improved photocatalytic activity might be attributed to the improved charge transfer and significant separation of the photoinduced electrons and holes in the presence of a two-dimensional graphene network. The results of recycling experiments show that RGO–TiO2 composites have a high photostability, which is expected in the practical application. Radical trapping experiments indicated that ·OH plays a crucial role in the process of AO7 degradation.


Graphene TiO2 RGO–TiO2 Photocatalytic Mechanism 



The authors gratefully acknowledge the financial support provided by the National Natural Science Foundation of China (Project No. 21107085). Partial supports by the Natural Science Foundation of Shaanxi Province (Project No. K3320215185) and the Fundamental Research Funds for the Central Universities (Project No. QN2013073) are also acknowledged.

Supplementary material

11356_2017_8927_MOESM1_ESM.doc (292 kb)
ESM 1 (DOC 292 kb)


  1. Asahi R, Morikawa T, Irie H, Ohwaki T (2014) Nitrogen-doped titanium dioxide as visible-light-sensitive photocatalyst: designs, developments, and prospects. Chem Rev 114:9824–9852CrossRefGoogle Scholar
  2. Bagheri S, Julkapli NM (2016) Synergistic effects on hydrogenated TiO2 for photodegradation of synthetic compounds pollutants. Int J Hydrog Energy 41:14652–14664CrossRefGoogle Scholar
  3. Balandin AA, Ghosh S, Bao W, Calizo I, Teweldebrhan D, Miao F, Lau CN (2008) Superior thermal conductivity of single-layer graphene. Nano Lett 8:902–907CrossRefGoogle Scholar
  4. Calza P, Hadjicostas C, Sakkas VA, Sarro M, Minero C, Medana C, Albanis TA (2016) Photocatalytic transformation of the antipsychotic drug risperidone in aqueous media on reduced graphene oxide-TiO2 composites. Appl Catal B 183:96–106CrossRefGoogle Scholar
  5. Chen D, Zou L, Li S, Zheng F (2016) Nanospherical like reduced graphene oxide decorated TiO2 nanoparticles: an advanced catalyst for the hydrogen evolution reaction. Sci Rep 6:1–8CrossRefGoogle Scholar
  6. Chen P, Zhu L, Fang S, Wang C, Shan G (2012) Photocatalytic degradation efficiency and mechanism of microcystin-RR by mesoporous Bi2WO6 under near ultraviolet light. Environ Sci Technol 46:2345–2351CrossRefGoogle Scholar
  7. Chen X, Mao S (2007) Titanium dioxide nanomaterials: synthesis properties modifications and applications. Chem Rev 107:2891–2959CrossRefGoogle Scholar
  8. Cheng B, Le Y, Yu J (2010) Preparation and enhanced photocatalytic activity of Ag@TiO2 core-shell nanocomposite nanowires. J Hazard Mater 177:971–977CrossRefGoogle Scholar
  9. Czech B, Buda W, Pasieczna-Patkowska S, Oleszczuk P (2015) MWCNT-TiO2-SiO2 nanocomposites possessing the photocatalytic activity in UVA and UVC. Appl Catal B 162:564–572CrossRefGoogle Scholar
  10. Dahl M, Liu Y, Yin Y (2014) Composite titanium dioxide nanomaterials. Chem Rev 114:9853–9889CrossRefGoogle Scholar
  11. Dolat D, Quici N, Kusiak-Nejman E, Morawski AW, Li Puma G (2012) One-step, hydrothermal synthesis of nitrogen, carbon co-doped titanium dioxide (N, C-TiO2) photocatalysts. Effect of alcohol degree and chain length as carbon dopant precursors on photocatalytic activity and catalyst deactivation. Appl Catal B 115:81–89CrossRefGoogle Scholar
  12. Fan W, Lai Q, Zhang Q, Wang Y (2011) Nanocomposites of TiO2 and reduced graphene oxide as efficient photocatalysts for hydrogen evolution. J Phys Chem C 115:10694–10701CrossRefGoogle Scholar
  13. Gaya UI, Abdullah AH (2008) Heterogeneous photocatalytic degradation of organic contaminants over titanium dioxide: a review of fundamentals, progress and problems. J Photochem Photobiol C 9:1–12CrossRefGoogle Scholar
  14. Geim AK, Novoselov KS (2007) The rise of graphene. Nat Mater 6:183–191CrossRefGoogle Scholar
  15. Hoffmann MR, Martin ST, Choi W, Bahnemann DW (1995) Environmental applications of semiconductor photocatalysis. Chem Rev 95:69–96CrossRefGoogle Scholar
  16. Hou C, Zhang Q, Li Y, Wang H (2012) P25-graphene hydrogels: room-temperature synthesis and application for removal of methylene blue from aqueous solution. J Hazard Mater 205:229–235CrossRefGoogle Scholar
  17. Hu J, Li H, Wu Q, Zhao Y, Jiao Q (2015) Synthesis of TiO2 nanowire/reduced graphene oxide nanocomposites and their photocatalytic performances. Chem Eng J 263:144–150CrossRefGoogle Scholar
  18. Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339–1339CrossRefGoogle Scholar
  19. Ji KH, Jang DM, Cho YJ, Myung Y, Kim HS, Kim Y, Park J (2009) Comparative photocatalytic ability of nanocrystal-carbon nanotube and TiO2 nanocrystal hybrid nanostructures. J Phys Chem C 113:19966–19972CrossRefGoogle Scholar
  20. 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 11:771–778CrossRefGoogle Scholar
  21. Kowalska E, Remita H, Colbeau-Justin C, Hupka J, Belloni J (2008) Modification of titanium dioxide with platinum ions and clusters: application in photocatalysis. J Phys Chem C 112:1124–1131CrossRefGoogle Scholar
  22. Lei M, Wang N, Zhu L, Xie C, Tang H (2014) A peculiar mechanism for the photocatalytic reduction of decabromodiphenyl ether over reduced graphene oxide-TiO2 photocatalyst. Chem Eng J 241:207–215CrossRefGoogle Scholar
  23. Li D, Mueller MB, Gilje S, Kaner RB, Wallace GG (2008) Processable aqueous dispersions of graphene nanosheets. Nat Nanotechnol 3:101–105CrossRefGoogle Scholar
  24. Li H, Xia Z, Chen J, Lei L, Xing J (2015) Constructing ternary CdS/reduced graphene oxide/TiO2 nanotube arrays hybrids for enhanced visible-light-driven photoelectrochemical and photocatalytic activity. Appl Catal B 168:105–113Google Scholar
  25. Li L, Yu L, Lin Z, Yang G (2016) Reduced TiO2-graphene oxide heterostructure as broad spectrum-driven efficient water-splitting photocatalysts. ACS Appl Mater Interfaces 8:8536–8545CrossRefGoogle Scholar
  26. Liu X, Pan L, Lv T, Zhu G, Sun Z, Sun C (2011) Microwave-assisted synthesis of CdS-reduced graphene oxide composites for photocatalytic reduction of Cr(VI). Chem Commun 47:11984–11986CrossRefGoogle Scholar
  27. Liu Y (2014) Hydrothermal synthesis of TiO 2–RGO composites and their improved photocatalytic activity in visible light. RSC Adv 4:36040–36045CrossRefGoogle Scholar
  28. Long M, Qin Y, Chen C, Guo X, Tan B, Cai W (2013) Origin of visible light photoactivity of reduced graphene oxide/TiO2 by in situ hydrothermal growth of undergrown TiO2 with graphene oxide. J Phys Chem C 117:16734–16741CrossRefGoogle Scholar
  29. Luan X, Wing MTG, Wang Y (2015) Enhanced photocatalytic activity of graphene oxide/titania nanosheets composites for methylene blue degradation. Mater Sci Semicond Process 30:592–598CrossRefGoogle Scholar
  30. Ma YZ, Stenger J, Zimmermann J, Bachilo SM, Smalley RE, Weisman RB, Fleming GR (2004) Ultrafast carrier dynamics in single walled carbon nanotubes probed by femtosecond spectroscopy. J Chem Phys 120:3368–3373CrossRefGoogle Scholar
  31. Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun Z, Slesarev A, Alemany LB, Lu W, Tour JM (2010) Improved synthesis of graphene oxide. ACS Nano 4:4806–4814CrossRefGoogle Scholar
  32. Miljevic M, Geiseler B, Bergfeldt T, Bockstaller P, Fruk L (2014) Enhanced photocatalytic activity of Au/TiO2 nanocomposite prepared using bifunctional bridging linker. Adv Funct Mater 24:907–915CrossRefGoogle Scholar
  33. Mills A, Davies RH, Worsley D (1993) Water purification by semiconductor photocatalysis. Chem Soc Rev 22:417–425CrossRefGoogle Scholar
  34. Morales-Torres S, Pastrana-Martinez LM, Figueiredo JL, Faria JL, Silva AMT (2013) Graphene oxide-P25 photocatalysts for degradation of diphenhydramine pharmaceutical and methyl orange dye. Appl Surf Sci 275:361–368CrossRefGoogle Scholar
  35. Moussa H, Girot E, Mozet K, Alem H, Medjahdi G, Schneider R (2016) ZnO rods/reduced graphene oxide composites prepared via a solvothermal reaction for efficient sunlight-driven photocatalysis. Appl Catal B 185:11–21CrossRefGoogle Scholar
  36. Murugan AV, Muraliganth T, Manthiram A (2009) Rapid, facile microwave-solvothermal synthesis of graphene nanosheets and their polyaniline nanocomposites for energy strorage. Chem Mater 21:5004–5006CrossRefGoogle Scholar
  37. Nainani RK, Thakur P (2016) Facile synthesis of TiO2-RGO composite with enhanced performance for the photocatalytic mineralization of organic pollutants. Water Sci Technol 73:1927–1936CrossRefGoogle Scholar
  38. Nethravathi C, Rajamathi M (2008) Chemically modified graphene sheets produced by the solvothermal reduction of colloidal dispersions of graphite oxide. Carbon 46:1994–1998CrossRefGoogle Scholar
  39. Pan X, Yang MQ, Tang ZR, Xu YJ (2014) Noncovalently functionalized graphene-directed synthesis of ultralarge graphene-based TiO2 nanosheet composites: tunable morphology and photocatalytic applications. J Phys Chem C 118:27325–27335CrossRefGoogle Scholar
  40. Pastrana-Martínez LM, Morales-Torres S, Likodimos V, Falaras P, Figueiredo JL, Faria JL, Silva AMT (2014) Role of oxygen functionalities on the synthesis of photocatalytically active grapheme-TiO2 composites. Appl Catal B 158:329–340CrossRefGoogle Scholar
  41. Qin N, Liu Y, Wu W, Shen L, Chen X, Li Z, Wu L (2015) One-dimensional CdS/TiO2 nanofiber composites as efficient visible-light-driven photocatalysts for selective organic transformation: synthesis, characterization, and performance. Langmuir 31:1203–1209CrossRefGoogle Scholar
  42. Tan LL, Chai SP, Mohamed AR (2012) Synthesis and applications of graphene-based TiO2 photocatalysts. ChemSusChem 5:1868–1882CrossRefGoogle Scholar
  43. Tu W, Zhou Y, Liu Q, Yan S, Bao S, Wang X, Xiao M, Zou Z (2013) An in situ simultaneous reduction-hydrolysis technique for fabrication of TiO2-graphene 2D sandwich-like hybrid nanosheets: graphene promoted selectivity of photocatalytic-driven hydrogenation and coupling of CO2 into methane and ethane. Adv Funct Mater 23:1743–1749CrossRefGoogle Scholar
  44. Umar M, Aziz HA (2013) Photocatalytic degradation of organic pollutants in water. In: Nageeb Rashed M (ed) Organic Pollutants–Monitoring, Risk and Treatment, 1st edn. In Tech, Croatia, pp 195–208Google Scholar
  45. Wang H, Zhang L, Chen Z, Hu J, Li S, Wang Z, Liu J, Wang X (2014) Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic performances. Chem Soc Rev 43:5234–5244CrossRefGoogle Scholar
  46. Wang J, Wang P, Cao Y, Chen J, Li W, Shao Y, Zheng Y, Li D (2013a) A high efficient photocatalyst Ag3VO4/TiO2/graphene nanocomposite with wide spectral response. Appl Catal B 136:94–102CrossRefGoogle Scholar
  47. Wang P, Wang J, Wang X, Yu H, Yu J, Lei M, Wang Y (2013b) One-step synthesis of easy-recycling TiO 2-rGO nanocomposite photocatalysts with enhanced photocatalytic activity. Appl Catal B 132:452–459CrossRefGoogle Scholar
  48. Woan K, Pyrgiotakis G, Sigmund W (2009) Photocatalytic carbon-nanotube-TiO2 composites. Adv Mater 21:2233–2239CrossRefGoogle Scholar
  49. Wu T, Cai X, Tan S, Li H, Liu J, Yang W (2011) Adsorption characteristics of acrylonitrile, p-toluenesulfonic acid, 1-naphthalenesulfonic acid and methyl blue on graphene in aqueous solutions. Chem Eng J 173:144–149CrossRefGoogle Scholar
  50. Xiang Q, Yu J, Jaroniec M (2012) Graphene-based semiconductor photocatalysts. Chem Soc Rev 41:782–796CrossRefGoogle Scholar
  51. Yao W, Li Y, Yan D, Ma M, He Z, Chai S, Su X, Chen F, Fu Q (2013) Fabrication and photocatalysis of TiO2-graphene sandwich nanosheets with smooth surface and controlled thickness. Chem Eng J 229:569–576CrossRefGoogle Scholar
  52. Yao Y, Li G, Ciston S, Lueptow RM, Gray KA (2008) Photoreactive TiO2/carbon nanotube composites: synthesis and reactivity. Environ Sci Technol 42:4952–4957CrossRefGoogle Scholar
  53. Yao Y, Lu F, Zhu Y, Wei F, Liu X, Lian C, Wang S (2015) Magnetic core-shell CuFe2O4@C3N4 hybrids for visible light photocatalysis of orange II. J Hazard Mater 297:224–233CrossRefGoogle Scholar
  54. Yu C, Li G, Kumar S, Kawasaki H, Jin R (2013) Stable Au25(Sr)18/TiO2 composite nanostructure with enhanced visible light photocatalytic activity. J Phys Chem Lett 4:2847–2852CrossRefGoogle Scholar
  55. Yu Y, Jimmy CY, Chan CY, Che YK, Zhao JC, Ding L, Ge WK, Wong PK (2005) Enhancement of adsorption and photocatalytic activity of TiO2 by using carbon nanotubes for the treatment of azo dye. Appl Catal B 61:1–11CrossRefGoogle Scholar
  56. Zanjanchi MA, Golmojdeh H, Arvand M (2009) Enhanced adsorptive and photocatalytic achievements in removal of methylene blue by incorporating tungstophosphoric acid-TiO2 into MCM-41. J Hazard Mater 169:233–239CrossRefGoogle Scholar
  57. Zhang H, Lv X, Li Y, Wang Y, Li J (2010) P25-graphene composite as a high performance photocatalyst. ACS Nano 4:380–386CrossRefGoogle Scholar
  58. Zhao F, Dong B, Gao R, Su G, Liu W, Shi L, Xia C, Cao L (2015) A three-dimensional graphene-TiO2 nanotube nanocomposite with exceptional photocatalytic activity for dye degradation. Appl Surf Sci 351:303–308CrossRefGoogle Scholar
  59. Zhou G, Guo J, Zhou G, Wan X, Shi H (2016) Photodegradation of orange II using waste paper sludge-derived heterogeneous catalyst in the presence of oxalate under ultraviolet light emitting diode irradiation. J Environ Sci 47:63–70CrossRefGoogle Scholar
  60. Zhou K, Zhu Y, Yang X, Jiang X, Li C (2011) Preparation of graphene-TiO2 composites with enhanced photocatalytic activity. New J Chem 35:353–359CrossRefGoogle Scholar
  61. Zhu G, Xu T, Lv T, Pan L, Zhao Q, Sun Z (2011) Graphene-incorporated nanocrystalline TiO2 films for CdS quantum dot-sensitized solar cells. J Electroanal Chem 650:248–251CrossRefGoogle Scholar
  62. Zhu M, Zhai C, Qiu L, Lu C, Paton AS, Du Y, Goh MC (2015) New method to synthesize s-doped TiO2 with stable and highly efficient photocatalytic performance under indoor sunlight irradiation. ACS Sustain Chem Eng 3:3123–3129CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • Tengfei Li
    • 1
  • Tiecheng Wang
    • 1
    • 2
  • Guangzhou Qu
    • 1
    • 2
    Email author
  • Dongli Liang
    • 1
    • 2
  • Shibin Hu
    • 1
    • 2
  1. 1.College of Natural Resources and EnvironmentNorthwest A&F UniversityYanglingPeople’s Republic of China
  2. 2.Key Laboratory of Plant Nutrition and the Agri-environment in Northwest China, Ministry of AgricultureYanglingPeople’s Republic of China

Personalised recommendations