Environmental Science and Pollution Research

, Volume 26, Issue 4, pp 3455–3464 | Cite as

Amalgamation of N-graphene quantum dots with nanocubic like TiO2: an insight study of sunlight sensitive photocatalysis

  • Ping Feng Lim
  • Kah Hon LeongEmail author
  • Lan Ching Sim
  • Azrina Abd Aziz
  • Pichiah Saravanan
Research Article


In this work, a sunlight-sensitive photocatalyst of nanocubic-like titanium dioxide (TiO2) and N-doped graphene quantum dots (N-GQDs) is developed through a simple hydrothermal and physical mixing method. The successful amalgamation composite photocatalyst characteristics were comprehensively scrutinized through various physical and chemical analyses. A complete removal of bisphenol A (BPA) is attained by a synthesized composite after 30 min of sunlight irradiation as compared to pure TiO2. This clearly proved the unique contribution of N-GQDs that enhanced the ability of light harvesting especially under visible light and near-infrared region. This superior characteristic enables it to maximize the absorbance in the entire solar spectrum. However, the increase of N-GQDs weight percentage has created massive oxygen vacancies that suppress the generation of active radicals. This resulted in a longer duration for a complete removal of BPA as compared to lower weight percentage of N-GQDs. Hence, this finding can offer a new insight in developing effective sunlight-sensitive photocatalysts for various complex organic pollutants degradation.


N-Graphene quantum dots Nanocubic-like TiO2 Bisphenol A Sunlight Visible light Near Infrared 



This research work was supported by the Universiti Tunku Abdul Rahman Research Fund, UTARRF (IPSR/RMC/UTARRF/2016-C2/L05).

Supplementary material

11356_2018_3821_MOESM1_ESM.docx (196 kb)
ESM 1 (DOCX 196 kb)


  1. Amorós-Pérez A, Cano-Casanova L, Lillo-Ródenas MÁ, Román-Martínez MC (2017) Cu/TiO2 photocatalysts for the conversion of acetic acid into biogas and hydrogen. Catal Today 287:78–84Google Scholar
  2. Bechambi O, Jlaiel L, Najjar W, Sayadi S (2016) Photocatalytic degradation of bisphenol A in the presence of Ce–ZnO: Evolution of kinetics, toxicity and photodegradation mechanism. Mater Chem Phys 173:95–105Google Scholar
  3. Chai S, Zhao G, Zhang YN, Wang Y, Nong F, Li M, Li D (2012) Selective photoelectrocatalytic degradation of recalcitrant contaminant driven by an nP heterojunction nanoelectrode with molecular recognition ability. Environ Sci Technol 46:10182–10190Google Scholar
  4. Chan DK, Cheung PL, Jimmy CY (2014) A visible-light-driven composite photocatalyst of TiO2 nanotube arrays and graphene quantum dots. Beilstein J Nanotechnol 5:689–695Google Scholar
  5. Chen Q, Zhang Y, Zhang D, Yang Y (2017) Ag and N co-doped TiO2 nanostructured photocatalyst for printing and dyeing wastewater. J Water Process Eng 16:14–20Google Scholar
  6. Chimmikuttanda SP, Naik A, Akple MS, Rajegowda RH (2017) Hydrothermal synthesis of TiO2 hollow spheres adorned with SnO2 quantum dots and their efficiency in the production of methanol via photocatalysis. Environ Sci Pollut Res 24:26436–26443Google Scholar
  7. Chong MN, Cho YJ, Poh PE, Jin B (2015) Evaluation of titanium dioxide photocatalytic technology for the treatment of reactive Black 5 dye in synthetic and real greywater effluents. J Clean Prod 89:196–202Google Scholar
  8. Chua CK, Sofer Z, Simek P, Jankovsky O, Klimova K, Bakardjieva S, Hrdličková Kučková S, Pumera M (2015) Synthesis of strongly fluorescent graphene quantum dots by cage-opening buckminsterfullerene. ACS Nano 9:2548–2555Google Scholar
  9. Das R, Dhar N, Bandyopadhyay A, Jana D (2016) Size dependent magnetic and optical properties in diamond shaped graphene quantum dots: a DFT study. J Phys Chem Solids 99:34–42Google Scholar
  10. Di Valentin C, Pacchioni G, Selloni A (2005) Theory of carbon doping of titanium dioxide. Chem Mater 17:6656–6665Google Scholar
  11. Dominguez S, Huebra M, Han C, Campo P, Nadagouda MN, Rivero MJ, Ortiz I, Dionysiou DD (2017) Magnetically recoverable TiO2-WO3 photocatalyst to oxidize bisphenol A from model wastewater under simulated solar light. Environ Sci Pollut Res 24:12589–12598Google Scholar
  12. Dong Y, Lin J, Chen Y, Fu F, Chi Y, Chen G (2014) Graphene quantum dots, graphene oxide, carbon quantum dots and graphite nanocrystals in coals. Nanoscale 6:7410–7415Google Scholar
  13. González-Pedro V, Zarazua I, Barea EM, Fabregat-Santiago F, de la Rosa E, Mora-Seró I, Giménez S (2014) Panchromatic solar-to-H2 conversion by a hybrid quantum dots–dye dual absorber tandem device. J Phys Chem C 118:891–895Google Scholar
  14. Grabowska E, Marchelek M, Klimczuk T, Lisowski W, Zaleska-Medynska A (2017) TiO2/SrTiO3 and SrTiO3 microspheres decorated with Rh, Ru or Pt nanoparticles: highly UV–vis responsible photoactivity and mechanism. J Catal 350:159–173Google Scholar
  15. Guerra P, Kim M, Teslic S, Alaee M, Smyth SA (2015) Bisphenol-A removal in various wastewater treatment processes: operational conditions, mass balance, and optimization. J Environ Manag 152:192–200Google Scholar
  16. Henderson MA (2011) A surface science perspective on photocatalysis. Surf Sci Rep 66:185–297Google Scholar
  17. Hund-Rinke K, Simon M (2006) Ecotoxic effect of photocatalytic active nanoparticles (TiO2) on algae and daphnids (8 pp). Environ Sci Pollut Res 13:225–232Google Scholar
  18. Huy NX, Phuong DTT, Van Minh N (2017) A study on structure, morphology, optical properties, and photocatalytic ability of SrTiO3/TiO2 granular composites. Phys B Condens Matter 532:37–41Google Scholar
  19. Kamisaka H, Adachi T, Yamashita K (2005) Theoretical study of the structure and optical properties of carbon-doped rutile and anatase titanium oxides. J Chem Phys 123:084704Google Scholar
  20. Kaur M, Verma NK (2014) CaCO3/TiO2 nanoparticles based dye sensitized solar cell. J Mater Sci Technol 30:328–334Google Scholar
  21. Lei ZD, Wang JJ, Wang L, Yang XY, Xu G, Tang L (2016) Efficient photocatalytic degradation of ibuprofen in aqueous solution using novel visible-light responsive graphene quantum dot/AgVO3 nanoribbons. J Hazard Mater 312:298–306Google Scholar
  22. Leong KH, Monash P, Ibrahim S, Saravanan P (2014) Solar photocatalytic activity of anatase TiO2 nanocrystals synthesized by non-hydrolitic sol–gel method. Sol Energy 101:321–332Google Scholar
  23. Li J, Wang Y, Tian Y, He X, Yang P, Yuan M, Cao Y, Lyu J (2018) Crystallization of microporous TiO2 through photochemical deposition of Pt for photocatalytic degradation of volatile organic compounds. Environ Sci Pollut Res 25:15662–15679Google Scholar
  24. Liu G, Ma J, Li X, Qin Q (2009) Adsorption of bisphenol A from aqueous solution onto activated carbons with different modification treatments. J Hazard Mater 164:1275–1280Google Scholar
  25. Mahmood T, Cao C, Tahir M, Idrees F, Ahmed M, Tanveer M, Aslam I, Usman Z, Ali Z, Hussain S (2013) Electronic, elastic, acoustic and optical properties of cubic TiO2: A DFT approach. Physica B 420:74–80Google Scholar
  26. Martins NC, Ângelo J, Girão AV, Trindade T, Andrade L, Mendes A (2016) N-doped carbon quantum dots/TiO2 composite with improved photocatalytic activity. Appl Catal B Environ 193:67–74Google Scholar
  27. Miloua R, Kebbab Z, Benramdane N, Khadraoui M, Chiker F (2011) Ab initio prediction of elastic and thermal properties of cubic TiO2. Comput Mater Sci 50:2142–2147Google Scholar
  28. Min S, Hou J, Lei Y, Ma X, Lu G (2017) Facile one-step hydrothermal synthesis toward strongly coupled TiO2/graphene quantum dots photocatalysts for efficient hydrogen evolution. Appl Surf Sci 396:1375–1382Google Scholar
  29. Palaniselvam T, Valappil MO, Illathvalappil R, Kurungot S (2014) Nanoporous graphene by quantum dots removal from graphene and its conversion to a potential oxygen reduction electrocatalyst via nitrogen doping. Energy Environ Sci 7:1059–1067Google Scholar
  30. Palominos R, Freer J, Mondaca MA, Mansilla HD (2008) Evidence for hole participation during the photocatalytic oxidation of the antibiotic flumequine. J Photochem Photobiol A-Chem 193:139–145Google Scholar
  31. Pan D, Zhang J, Li Z, Wu M (2010) Hydrothermal route for cutting graphene sheets into blue luminescent graphene quantum dots. Adv Mater 22:734–738Google Scholar
  32. Pan D, Jiao J, Li Z, Guo Y, Feng C, Liu Y, Wang L, Wu M (2015) Efficient separation of electron–hole pairs in graphene quantum dots by TiO2 heterojunctions for dye degradation. ACS Sustain Chem Eng 3:2405–2413Google Scholar
  33. Park H, Park Y, Kim W, Choi W (2013) Surface modification of TiO2 photocatalyst for environmental applications. J Photochem Photobiol C 15:1–20Google Scholar
  34. Pelaez M, Nolan NT, Pillai SC, Seery MK, Falaras P, Kontos AG, Dunlop PS, Hamilton JW, Byrne JA, O'shea K, Entezari MH (2012) A review on the visible light active titanium dioxide photocatalysts for environmental applications. Appl Catal B Environ 125:331–349Google Scholar
  35. Qu D, Zheng M, Du P, Zhou Y, Zhang L, Li D, Tan H, Zhao Z, Xie Z, Sun Z (2013) Highly luminescent S, N co-doped graphene quantum dots with broad visible absorption bands for visible light photocatalysts. Nanoscale 5:12272–12277Google Scholar
  36. Qu A, Xie H, Xu X, Zhang Y, Wen S, Cui Y (2016) High quantum yield graphene quantum dots decorated TiO2 nanotubes for enhancing photocatalytic activity. Appl Surf Sci 375:230–241Google Scholar
  37. Rajabi HR, Farsi M (2015) Effect of transition metal ion doping on the photocatalytic activity of ZnS quantum dots: synthesis, characterization, and application for dye decolorization. J Mol Catal A Chem 399:53–61Google Scholar
  38. Rajabi HR, Farsi M (2016) Study of capping agent effect on the structural, optical and photocatalytic properties of zinc sulfide quantum dots. Mater Sci Semicond Process 48:14–22Google Scholar
  39. Rajabi HR, Khani O, Shamsipur M, Vatanpour V (2013) High-performance pure and Fe3+-ion doped ZnS quantum dots as green nanophotocatalysts for the removal of malachite green under UV-light irradiation. J Hazard Mater 250:370–378Google Scholar
  40. Ribao P, Rivero MJ, Ortiz I (2017) TiO2 structures doped with noble metals and/or graphene oxide to improve the photocatalytic degradation of dichloroacetic acid. Environ Sci Pollut Res 24:12628–12637Google Scholar
  41. Rodenas P, Song T, Sudhagar P, Marzari G, Han H, Badia-Bou L, Gimenez S, Fabregat Santiago F, Mora Sero I, Bisquert J, Paik U (2013) Quantum dot based heterostructures for unassisted photoelectrochemical hydrogen generation. Adv Energy Mater 3:176–182Google Scholar
  42. Roushani M, Mavaei M, Rajabi HR (2015) Graphene quantum dots as novel and green nano-materials for the visible-light-driven photocatalytic degradation of cationic dye. J Mol Catal A Chem 409:102–109Google Scholar
  43. Roy N, Sohn Y, Pradhan D (2013) Synergy of low-energy {101} and high-energy {001} TiO2 crystal facets for enhanced photocatalysis. ACS Nano 7:2532–2540Google Scholar
  44. Safardoust-Hojaghan H, Salavati-Niasari M (2017) Degradation of methylene blue as a pollutant with N-doped graphene quantum dot/titanium dioxide nanocomposite. J Clean Prod 148:31–36Google Scholar
  45. Shen K, Xue X, Wang X, Hu X, Tian H, Zheng W (2017) One-step synthesis of band-tunable N, S co-doped commercial TiO2/graphene quantum dots composites with enhanced photocatalytic activity. RSC Adv 7:23319–23,327Google Scholar
  46. Taheri ME, Petala A, Frontistis Z, Mantzavinos D, Kondarides DI (2017) Fast photocatalytic degradation of bisphenol A by Ag3PO4/TiO2 composites under solar radiation. Catal Today 280:99–107Google Scholar
  47. Tian H, Shen K, Hu X, Qiao L, Zheng W (2017) N, S co-doped graphene quantum dots-graphene-TiO2 nanotubes composite with enhanced photocatalytic activity. J Alloys Compd 691:369–377Google Scholar
  48. Wang G, Wang H, Ling Y, Tang Y, Yang X, Fitzmorris RC, Wang C, Zhang JZ, Li Y (2011) Hydrogen-treated TiO2 nanowire arrays for photoelectrochemical water splitting. Nano Lett 11:3026–3033Google Scholar
  49. Wang J, Li C, Cong J, Liu Z, Zhang H, Liang M, Gao J, Wang S, Yao J (2016) Facile synthesis of nanorod-type graphitic carbon nitride/Fe2O3 composite with enhanced photocatalytic performance. J Solid State Chem 238:246–251Google Scholar
  50. Wu W, Shan G, Wang S, Zhu L, Yue L, Xiang Q, Zhang Y, Li Z (2016) Environmentally relevant impacts of nano-TiO2 on abiotic degradation of bisphenol A under sunlight irradiation. Environ Pollut 216:166–172Google Scholar
  51. Xie H, Hou C, Wang H, Zhang Q, Li Y (2017) S, N Co-doped graphene quantum dot/TiO2 composites for efficient photocatalytic hydrogen generation. Nanoscale Res Lett 12:400Google Scholar
  52. Xu Q, Yu J, Zhang J, Zhang J, Liu G (2015) Cubic anatase TiO2 nanocrystals with enhanced photocatalytic CO2 reduction activity. Chem Commun 51:7950–7953Google Scholar
  53. Yamanaka H, Moriyoshi K, Ohmoto T, Ohe T, Sakai K (2008) Efficient microbial degradation of bisphenol A in the presence of activated carbon. J Biosci Bioeng 105:157–160Google Scholar
  54. Yu S, Zhong YQ, Yu BQ, Cai SY, Wu LZ, Zhou Y (2016) Graphene quantum dots to enhance the photocatalytic hydrogen evolution efficiency of anatase TiO2 with exposed {001} facet. Phys Chem Chem Phys 18:20338–20344Google Scholar
  55. Zhang Y, Qi F, Li Y, Zhou X, Sun H, Zhang W, Liu D, Song XM (2017) Graphene oxide quantum dot-sensitized porous titanium dioxide microsphere: Visible-light-driven photocatalyst based on energy band engineering. J Colloid Interface Sci 498:105–111Google Scholar
  56. Zhao L, Xiao X, Peng L, Gu FL, Zhang RQ (2014) Visible-light photocatalytic mechanism of bisphenol-A on nano-Bi2O3: a combined DFT calculation and experimental study. RSC Adv 4:10343–10349Google Scholar
  57. Zhu H, Liu A, Xu Y, Shan F, Li A, Wang J, Yang W, Barrow C, Liu J (2015) Graphene quantum dots directly generated from graphite via magnetron sputtering and the application in thin-film transistors. Carbon 88:225–232Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Environmental Engineering, Faculty of Engineering and Green TechnologyUniversiti Tunku Abdul RahmanKamparMalaysia
  2. 2.Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and ScienceUniversiti Tunku Abdul RahmanKajangMalaysia
  3. 3.Department of Energy and Environment, Faculty of Engineering TechnologyUniversiti Malaysia PahangKuantanMalaysia
  4. 4.Environmental Nanotechnology Laboratory, Department of Environmental Science and EngineeringIndian Institute of Technology (ISM)DhanbadIndia

Personalised recommendations