Journal of Materials Science

, Volume 53, Issue 17, pp 12103–12114 | Cite as

Graphene quantum dots-assisted exfoliation of graphitic carbon nitride to prepare metal-free zero-dimensional/two-dimensional composite photocatalysts

Chemical routes to materials
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Abstract

The high aspect-ratio morphology of two-dimensional (2D) nanostructures endues them with distinct advantages for photocatalytic or photoelectrical applications. Although various attempts have been devoted to the liquid exfoliation of graphitic carbon nitride (g-C3N4) to obtain ultrathin nanosheets (CNNSs), the high exfoliation efficiency, well preservation of in-planar structure and facile operation cannot be simultaneously realized. Furthermore, functionalization of CNNSs is highly desired to promote the capability of photoabsorption, charge separation and transfer. Herein, we one-step prepared well-dispersed graphene quantum dots (GQDs)-modified CNNSs (GQDs/CNNSs) colloids via a facile and efficient GQDs-assisted exfoliation approach in a normal ultrasonic water bath. The exfoliation procedure was optimized by tuning the dopant in GQDs, ultrasonic time and GQDs dosage. The obtained colloidal GQDs/CNNSs show a typical 2D morphology with lateral size of several 100 nm and ultrathin thickness of 1.5–1.8 nm. What is more, we can tailor the semiconductive behavior of GQDs by heteroatom doping and achieve a pn-type P-doped GQDs-modified CNNSs colloids. This pn GQDs/CNNSs material presents the enhanced separation efficiency of photoexcited carriers and photocatalytic activity in comparison with bulky g-C3N4 (CN) and other CNNSs materials from acid or alkali exfoliation.

Notes

Acknowledgements

This work was financially supported from the financial support from the National Natural Science Foundation of China (No. 21305127), Zhejiang Provincial Natural Science Foundation of China (Nos. LY17B010004, LY17B050007) and the 521 talent project of ZSTU.

Supplementary material

10853_2018_2509_MOESM1_ESM.docx (2.7 mb)
Supplementary material 1 (DOCX 2771 kb)

References

  1. 1.
    Novoselov KS, Jiang D, Schedin F, Booth TJ, Khotkevich VV, Morozov SV, Geim AK (2005) Two-dimensional atomic crystals. PNAS 102:10451–10453CrossRefGoogle Scholar
  2. 2.
    Geim AK, Novoselov KS (2007) The rise of graphene. Nat Mater 6:183–191CrossRefGoogle Scholar
  3. 3.
    Karunadasa H, Motalvo E, Sun Y, Majda M, Long J, Chang C (2012) A molecular MoS2 edge site mimic for catalytic hydrogen generation. Science 335:698–792CrossRefGoogle Scholar
  4. 4.
    Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV (2004) Electric field effect in atomically thin carbon film. Science 306:666–669CrossRefGoogle Scholar
  5. 5.
    Chhowalla M, Shin HS, Eda G, Li LJ, Loh KP, Zhang H (2013) The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat Chem 5:263–275CrossRefGoogle Scholar
  6. 6.
    Xu K, Chen P, Li X, Wu C, Guo Y, Zhao J, Wu X, Xie Y (2013) Ultrathin nanosheets of vanadium diselenide: a metallic two-dimensional material with ferromagnetic charge-density-wave behavior. Angew Chem Int Ed 52:10477–10481CrossRefGoogle Scholar
  7. 7.
    Peng L, Peng X, Liu B, Wu C, Xie Y, Yu G (2013) Ultrathin two-dimensional MnO2/graphene hybrid nanostructures for high-performance, flexible planar supercapacitors. Nano Lett 13:2151–2157CrossRefGoogle Scholar
  8. 8.
    Zhu J, Li Q, Bi W, Bai L, Zhang X, Zhou J, Xie Y (2013) Ultra-rapid microwave-assisted synthesis of layered ultrathin birnessite K 0.17 MnO2 nanosheets for efficient energy storage. J Mater Chem A 1:8154–8159CrossRefGoogle Scholar
  9. 9.
    Rui X, Lu Z, Yin Z, Sim DH, Xiao N, Lim TM, Hng HH, Zhang H, Yan Q (2013) Oriented molecular attachments through sol–gel chemistry for synthesis of ultrathin hydrated vanadium pentoxide nanosheets and their applications. Small 9:716–721CrossRefGoogle Scholar
  10. 10.
    Liu L, Park J, Siegel D, McCarty K, Clark K, Deng W, Basile L, Idrobo JC, Li AP, Gu G (2014) Heteroepitaxial growth of two-dimensional hexagonal boron nitride template by graphene edges. Science 343:163–167CrossRefGoogle Scholar
  11. 11.
    Rousseas M, Goldstein AP, Mickelson W, Worsley MA, Woo L, Zettl A (2013) Synthesis of highly crystalline sp 2-bonded boron nitride aerogels. ACS Nano 7:8540–8546CrossRefGoogle Scholar
  12. 12.
    Yang D, Lu Z, Rui X, Huang X, Li H, Zhu J, Zhang W, Lam YM, Hng HH, Zhang H, Yan Q (2014) Synthesis of two-dimensional transition metal phosphates with highly ordered mesoporous structures for lithium-ion battery application. Angew Chem Int Ed 53:9352–93355CrossRefGoogle Scholar
  13. 13.
    Jiang Z, Li J, Aslan H, Li Q, Li Y, Chen M, Huang Y, Froning JP, Otyepka M, Zboril R, Besenbacher F, Dong M (2014) A high efficiency H2S gas sensor material: paper like Fe2O3/graphene nanosheets and structural alignment dependency of device efficiency. J Mater Chem A 2:6714–6717CrossRefGoogle Scholar
  14. 14.
    Lin C, Zhu X, Feng J, Wu C, Hu S, Peng L, Zhao J, Huang J, Yang J, Xie Y (2013) Hydrogen-incorporated TiS2 ultrathin nanosheets with ultrahigh conductivity for stamp-transferrable electrodes. J Am Chem Soc 135:5144–5151CrossRefGoogle Scholar
  15. 15.
    Zhong H, Yang G, Song H, Liao Q, Cui H, Shen P, Wang C (2012) Vertically aligned graphene-like SnS2 ultrathin nanosheet arrays: excellent energy storage, catalysis, photoconduction, and field-emitting performances. J Phys Chem C 116:9319–9326CrossRefGoogle Scholar
  16. 16.
    Voiry D, Fullon R, Yang J, e Silva CDCC, Kappera R, Bozkurt I, Kaplan D, Lagos MJ, Baston PE, Gupta G, Mohite AD (2016) The role of electronic coupling between substrate and 2D MoS2 nanosheets in electrocatalytic production of hydrogen. Nat Mater 15:1003–1009CrossRefGoogle Scholar
  17. 17.
    She X, Xu H, Xu Y, Yan J, Xia J, Xu L, Song Y, Jiang Y, Zhang Q, Li H (2014) Exfoliated graphene-like carbon nitride in organic solvents: enhanced photocatalytic activity and highly selective and sensitive sensor for the detection of trace amounts of Cu2+. J Mater Chem A 2:2563–2570CrossRefGoogle Scholar
  18. 18.
    Fu J, Tian Y, Chang B, Xi F, Dong X (2012) BiOBr-carbon nitride heterojunctions: synthesis, enhanced activity and photocatalytic mechanism. J Mater Chem 22:21159–21166CrossRefGoogle Scholar
  19. 19.
    Tian Y, Chang B, Lu J, Fu F, Xi F, Dong X (2013) Hydrothermal synthesis of graphitic carbon nitride-Bi2WO6 heterojunctions with enhanced visible light photocatalytic activities. ACS Appl Mater Interfaces 5:7079–7085CrossRefGoogle Scholar
  20. 20.
    Zhang Y, Zhou Z, Shen Y, Zhou Q, Wang J, Liu A, Liu S, Zhang Y (2016) Reversible assembly of graphitic carbon nitride 3D network for highly selective dyes absorption and regeneration. ACS Nano 10:9036–9043CrossRefGoogle Scholar
  21. 21.
    Yan J, Han X, Qian J, Liu J, Dong X, Xi F (2017) Preparation of 2 D graphitic carbon nitride nanosheets by a green exfoliation approach and the enhanced photo catalytic performance. J Mater Sci 52:13091–13102.  https://doi.org/10.1007/s10853-017-1419-5 CrossRefGoogle Scholar
  22. 22.
    Dong X, Cheng F (2015) Recent development in exfoliated two-dimensional g-C3N4 nanosheets for photocatalytic applications. J Mater Chem A 3:23642–23652CrossRefGoogle Scholar
  23. 23.
    Dong F, Li Y, Wang X, Wang Z, Ho WK (2015) Enhanced visible light photocatalytic activity and oxidation ability of porous graphene-like g-C3N4 nanosheets via thermal exfoliation. Appl Surf Sci 358:393–403CrossRefGoogle Scholar
  24. 24.
    Wang X, Maeda K, Thomas A, Takanabe K, Xin G, Carlsson J, Domen K, Antonietti M (2009) A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat Mater 8:76–80CrossRefGoogle Scholar
  25. 25.
    Kong L, Dong Y, Jiang P, Wang G, Zhang H, Zhao N (2016) Light-assisted rapid preparation of a Ni/g-C3N4 magnetic composite for robust photocatalytic H2 evolution from water. J Mater Chem A 4:9998–10007CrossRefGoogle Scholar
  26. 26.
    Xu L, Huang W, Wang L, Tian Z, Hu W, Ma Y, Wang X (2015) Insights into enhanced visible-light photocatalytic hydrogen evolution of g-C3N4 and highly reduced graphene oxide composite: the role of oxygen. Chem Mater 27:1612–1621CrossRefGoogle Scholar
  27. 27.
    Kumar A, Schuerings C, Kumar S, Kumar A, Krishnan V (2018) Perovskite-structured CaTiO3 coupled with g-C3N4 as a heterojunction photocatalyst for organic pollutant degradation. Beilstein J. Nanotechnol 9:671–685CrossRefGoogle Scholar
  28. 28.
    Kumar S, Kumar A, Kumar A, Balaji R, Krishnan V (2018) Highly efficient visible light active 2D–2D nanocomposites of N-ZnO–g-C3N4 for photocatalytic degradation of diverse industrial pollutants. ChemistrySelect 3:1919–1932CrossRefGoogle Scholar
  29. 29.
    Ye Y, Zhao Z, Hu Z, Liu L, Ji H, Shen Z, Ma T (2017) 0D/2D Heterojunctions of vanadate quantum dots/graphitic carbon nitride nanosheets for enhanced visible-light-driven photocatalysis. Angew Chem Int Ed 56:8407–8411CrossRefGoogle Scholar
  30. 30.
    Zhou L, Zhang H, Guo X, Sun H, Liu S, Tade M, Wang S (2017) Metal-free hybrids of graphitic carbon nitride and nanodiamonds for photoelectrochemical and photocatalytic applications. J Colloid Interface Sci 493:275–280CrossRefGoogle Scholar
  31. 31.
    Zhou L, Zhang H, Sun H, Liu S, Tade M, Wang S, Jin W (2016) Recent advances in non-metal modification of graphitic carbon nitride for photocatalysis: a historic review. Catal Sci Technol 6:7002–7023CrossRefGoogle Scholar
  32. 32.
    Liu S, Sun H, O’Donnell K, Ang H, Tade M, Wang S (2016) Metal-free melem/g-C3N4 hybrid photocatalysts for water treatment. J Colloid Interface Sci 464:10–17CrossRefGoogle Scholar
  33. 33.
    Niu P, Zhang L, Liu G, Cheng H (2012) Graphene-like carbon nitride nanosheets for improved photocatalytic activities. Adv Funct Mater 22:4763–4770CrossRefGoogle Scholar
  34. 34.
    Lu X, Xu K, Cheng P, Jia K, Liu S, Wu C (2014) Facile one step method realizing scalable production of g-C3N4 nanosheets and study of their photocatalytic H2 evolution activity. J Mater Chem A 2:18924–18928CrossRefGoogle Scholar
  35. 35.
    Yan J, Zhou C, Li P, Chen B, Zhang S, Xi F, Dong X, Liu J (2016) Nitrogen-rich graphitic carbon nitride: controllable nanosheet-like morphology, enhanced visible light absorption and superior photocatalytic performance. Colloids Surf A 508:257–264CrossRefGoogle Scholar
  36. 36.
    Tian Y, Chang B, Yang Z, Zhou B, Xi F, Dong X (2014) Graphitic carbon nitride-BiVO4 heterojunctions: simple hydrothermal synthesis and high photo catalytic performances. RSC Adv 4:4187–4193CrossRefGoogle Scholar
  37. 37.
    Chen B, Li P, Zhang S, Zhang W, Xi F, Dong X, Liu J (2016) The enhanced photocatalytic performance of Z-scheme two-dimensional/two-dimensional heterojunctions from graphitic carbon nitride nanosheets and titania nanosheets. J Colloid Interface Sci 478:263–270CrossRefGoogle Scholar
  38. 38.
    Kumar S, Reddy N, Kumar A, Shankar M, Krishnan V (2017) Two dimensional N-doped ZnO-graphitic carbon nitride nanosheets heterojunctions with enhanced photocatalytic hydrogen evolution. Int J Hydrogen Energy 8:3988–4002Google Scholar
  39. 39.
    Zhang X, Xie X, Wang H, Zhang J, Pan B, Xie Y (2013) Enhanced photoresponsive ultrathin graphitic-phase C3N4 nanosheets for bioimaging. J Am Chem Soc 135:18–21CrossRefGoogle Scholar
  40. 40.
    Yang S, Gong Y, Zhang J, Zhan L, Ma L, Fang Z, Vajtai R, Wang X, Ajayan PM (2013) Exfoliated graphitic carbon nitride nanosheets as efficient catalysts for hydrogen evolution under visible light. Adv Mater 25:2452–2456CrossRefGoogle Scholar
  41. 41.
    Xu J, Zhang L, Shi R, Zhu Y (2013) Chemical exfoliation of graphitic carbon nitride for efficient heterogeneous photocatalysis. J Mater Chem A 1:14766–14772CrossRefGoogle Scholar
  42. 42.
    Cheng F, Wang H, Dong X (2015) The amphoteric properties of g-C3N4 nanosheets and fabrication of their relevant heterostructure photocatalysts by an electrostatic re-assembly route. Chem Commun 51:7176–7179CrossRefGoogle Scholar
  43. 43.
    Cheng F, Yan J, Zhou C, Chen B, Li P, Chen Z, Dong X (2016) An alkali treating strategy for the colloidization of graphitic carbon nitride and its excellent photocatalytic performance. J Colloid Interface Sci 468:103–109CrossRefGoogle Scholar
  44. 44.
    Zheng X, Ananthanarayanan A, Luo K, Chen P (2014) Glowing graphene quantum dots and carbon dots: properties, syntheses, and biological applications. Small 11:1620–1636CrossRefGoogle Scholar
  45. 45.
    Peng J, Gao W, Gupta B, Liu Z, Romero-Aburto R, Ge L, Song L, Alemany L, Zhan X, Gao G, Vithaythil S, Kaipparettu B, Marti A, Hayashi T, Zhu J, Ajayan P (2012) Graphene quantum dots derived from carbon fibers. Nano Lett 12:844–849CrossRefGoogle Scholar
  46. 46.
    Zheng X, Than A, Ananthanarayanan A, Kim D, Chen P (2013) Graphene quantum dots as universal fluorophores and their use in revealing regulated trafficking of insulin receptors in adipocytes. ACS Nano 7:6278–6286CrossRefGoogle Scholar
  47. 47.
    Shen C, Ge S, Pang Y, Xi F, Liu J, Dong X, Chen P (2017) Facile and scalable preparation of highly luminescent N, S co-doped graphene quantum dots and their application for parallel detection of multiple metal ions. J Mater Chem B 5:6593–6600CrossRefGoogle Scholar
  48. 48.
    Shen J, Zhu Y, Yang X, Li C (2012) Graphene quantum dots: emergent nanolights for bioimaging sensors, catalysis and photovoltaic devices. Chem Commun 48:3686–3699CrossRefGoogle Scholar
  49. 49.
    Liu Y, Dong X, Chen P (2012) Biological and chemical sensors based on graphene materials. Chem Soc Rev 41:2283–2307CrossRefGoogle Scholar
  50. 50.
    Bian S, Shen C, Qian Y, Liu J, Xi F, Dong X (2017) Facile synthesis of sulfur-doped graphene quantum dots as fluorescent sensing probes for Ag+ ions detection. Sens Actuators B 242:231–237CrossRefGoogle Scholar
  51. 51.
    Bian S, Zhou C, Li P, Liu J, Dong X, Xi F (2017) Graphene quantum dots decorated titania nanosheets heterojunction: efficient charge separation and enhanced visible-light photocatalytic performance. Chemcatchem 9:3349–3357CrossRefGoogle Scholar
  52. 52.
    Lei Y, Yang C, Hou J, Wang F, Min S, Ma X, Jin Z, Xu J, Lu G, Huang K (2017) Strongly coupled CdS/graphene quantum dots nanohybrids for highly efficient photocatalytic hydrogen evolution: unraveling the essential roles of graphene quantum dots. Appl Catal B 216:59–69CrossRefGoogle Scholar
  53. 53.
    Yan M, Hua Y, Zhu F, Gu W, Jiang J, Shen H, Shi W (2017) Fabrication of nitrogen doped graphene quantum dots-BiOI/MnNb2O6 pn junction photocatalysts with enhanced visible light efficiency in photocatalytic degradation of antibiotics. Appl Catal B 202:518–527CrossRefGoogle Scholar
  54. 54.
    Kumar S, Dhiman A, Sudhagar P, Krishnan V (2018) ZnO-graphene quantum dots heterojunctions for natural sunlight-driven photocatalytic environmental remediation. Appl Surf Sci.  https://doi.org/10.1016/j.apsusc.2018.04.045 Google Scholar
  55. 55.
    Wang L, Wang Y, Xu T, Pan D, Sun L, Wu M (2014) Gram-scale synthesis of single-crystalline graphene quantum dots with superior optical properties. Nat Commun 5:5357CrossRefGoogle Scholar
  56. 56.
    Yan J, Han X, Zheng Z, Qian J, Liu J, Dong X, Xi F (2017) One-step template/chemical blowing route to synthesize flake-like porous carbon nitride photocatalyst. Mater Res Bull 94:423–427CrossRefGoogle Scholar
  57. 57.
    Yang Z, Li J, Cheng F, Chen Z, Dong X (2015) BiOBr/protonated graphitic C3N4 heterojunctions: intimate interfaces by electrostatic interaction and enhanced photocatalytic activity. J Alloys Compd 634:215–222CrossRefGoogle Scholar
  58. 58.
    Wang Y, Hong J, Zhang W, Xu R (2013) Carbon nitride nanosheets for photocatalytic hydrogen evolution: remarkably enhanced activity by dye sensitization. Catal Sci Technol 3:1703–1711CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.Department of ChemistryZhejiang Sci-Tech UniversityHangzhouChina

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