Porous oxygen-doped carbon nitride: supramolecular preassembly technology and photocatalytic degradation of organic pollutants under low-intensity light irradiation

  • Yuxiong Wang
  • Lei RaoEmail author
  • Peifang WangEmail author
  • Yong Guo
  • Xiang Guo
  • Lixin Zhang
Research Article


In order to overcome photocatalytic technology application limitations in water due to weak light intensity, it is crucial to synthesize photocatalysts that respond to weak light. In this study, porous and oxygen-doped carbon nitride (CN-MC) was synthesized via supramolecular preassembly technology using melamine and cyanuric chloride. The carbon nitride catalyst produced via this technology has a relatively high surface area (63.2 m2 g−1), irregular pores, and oxygen doping characteristics, which enhance the light capture capacity, increase the number of reactive sites, and accelerate electron–hole separation efficiency. Thus, the CN-MC exhibited excellent photocatalytic activity during the degradation of organic pollutants Rhodamine B (RhB, 95% removal within 6 h) and tetracycline hydrochloride (TC-HCl, 70% removal within 6 h) under low-intensity light (the light intensity = 0.8~1.8 mW cm−2 with a wavelength range of 300–700 nm). Mechanistic analysis showed that ·O2 and ·OH were the dominant active free radicals during RhB and TC-HCl photocatalytic degradation over CN-MC. The proposed synthesis strategy effectively improves the photocatalytic activity of graphite carbon nitride under weak light by producing a porous morphology and oxygen atom doping.


Carbon nitride Weak light Porous Oxygen doped Photocatalysis Supramolecular preassembly 


Funding information

This work received grants from the National Science Funds for Creative Research Groups of China (No. 51421006), the National Natural Science Foundation of China (No. 51775167), the National Major Projects of Water Pollution Control and Management Technology (No. 2017ZX07204003), and the Qing Lan Project of Jiangsu province.

Supplementary material

11356_2019_4800_MOESM1_ESM.doc (2.2 mb)
ESM 1 (DOC 2233 kb)


  1. Briggs D, Beamson G (1993) XPS studies of the oxygen 1s and 2s levels in a wide range of functional polymers. Anal Chem 65(11):1517–1523. CrossRefGoogle Scholar
  2. Cui YJ, Ding ZX, Liu P, Antonietti M, Fu XZ, Wang XC (2012) Metal-free activation of H2O2 by g-C3N4 under visible light irradiation for the degradation of organic pollutants. Phys Chem Chem Phys 14(4):1455–1462. CrossRefGoogle Scholar
  3. Cui YJ, Li M, Wang H, Yang CF, Meng SG, Chen FY (2018) In-situ synthesis of sulfur doped carbon nitride microsphere for outstanding visible light photocatalytic Cr (VI) reduction. Sep Purif Technol 199:251–259. CrossRefGoogle Scholar
  4. Ding Y, Tang Y, Yang L, Zeng Y, Yuan J, Liu T, Zhang S, Liu C, Luo S (2016) Porous nitrogen-rich carbon materials from carbon self-repairing g-C3N4 assembled with graphene for high-performance supercapacitor. J Mater Chem A 4(37):14307–14315. CrossRefGoogle Scholar
  5. Dong G, Zhao K, Zhang L (2012) Carbon self-doping induced high electronic conductivity and photoreactivity of g-C3N4. Chem Commun 48(49):6178–6180. CrossRefGoogle Scholar
  6. Dontsova D, Pronkin S, Wehle M, Chen ZP, Fettkenhauer C, Clavel G, Antonietti M (2015) Triazoles: a new class of precursors for the synthesis of negatively charged carbon nitride derivatives. Chem Mater 27(15):5170–5179. CrossRefGoogle Scholar
  7. Fan Y, Ai ZH, Zhang LZ (2010) Design of an electro-Fenton system with a novel sandwich film cathode for wastewater treatment. J Hazard Mater 176(1):678–684. CrossRefGoogle Scholar
  8. Frisch MJ, Trucks GW, Schlegel HB et al (2009) Gaussian 09, Revision A.02. Gaussian, Inc., WallingfordGoogle Scholar
  9. Fu J, Zhu B, Jiang C, Cheng B, You W, Yu J (2017) Hierarchical porous O-doped g-C3N4 with enhanced photocatalytic CO2 reduction activity. Small 13(15).
  10. Guo SE, Deng ZP, Li MX, Jiang BJ, Tian CG, Pan QJ, Fu HG (2016a) Phosphorus-doped carbon nitride tubes with a layered micro-nanostructure for enhanced visible-light photocatalytic hydrogen evolution. Angew Chem Int Ed 55(5):1830–1834. CrossRefGoogle Scholar
  11. Guo YF, Li J, Yuan YP, Li L, Zhang MY, Zhou CY, Lin ZQ (2016b) A rapid microwave-assisted thermolysis route to highly crystalline carbon nitrides for efficient hydrogen generation. Angew Chem Int Ed 55(47):14693–14697. CrossRefGoogle Scholar
  12. Guo Y, Wang RX, Wang PF, Li Y, Wang C (2017) Developing polyetherimide/graphitic carbon nitride floating photocatalyst with good photodegradation performance of methyl orange under light irradiation. Chemosphere 179:84–91. CrossRefGoogle Scholar
  13. Jan JZ, Huang BH, Lin JJ (2003) Facile preparation of amphiphilic oxyethylene-oxypropylene block copolymers by selective triazine coupling. Polymer 44(4):1003–1011. CrossRefGoogle Scholar
  14. Jiang LB, Yuan XZ, Zeng GM, Chen XH, Wu ZB, Liang J, Zhang J, Wang H, Wang H (2017a) Phosphorus- and sulfur-codoped g-C3N4: facile preparation, mechanism insight, and application as efficient photocatalyst for tetracycline and methyl orange degradation under visible light irradiation. ACS Sustain Chem Eng 5:5831–5841. CrossRefGoogle Scholar
  15. Jiang ZL, Li YM, Wang M, Liu D, Yuan J, Chen MZ, Wang J, Newkome GR, Sun W, Li XP, Wang PS (2017b) Constructing high-generation sierpiński triangles by molecular puzzling. Angew Chem Int Ed 56(38):11450–11455. CrossRefGoogle Scholar
  16. Jun YS, Lee EZ, Wang XC, Hong WH, Stucky GD, Thomas A (2013a) From melamine-cyanuric acid supramolecular aggregates to carbon nitride hollow spheres. Adv Funct Mater 23(29):3661–3667. CrossRefGoogle Scholar
  17. Jun YS, Park J, Lee SU, Thomas A, Hong WH, Stucky GD (2013b) Three-dimensional macroscopic assemblies of low-dimensional carbon nitrides for enhanced hydrogen evolution. Angew Chem Int Ed 52(42):11083–11087. CrossRefGoogle Scholar
  18. Kessler FK, Zheng Y, Schwarz D, Merschjann C, Schnick W, Wang XC, Bojdys MJ (2017) Functional carbon nitride materials–design strategies for electrochemical devices. Nat Rev Mats 2:17030. CrossRefGoogle Scholar
  19. Kumar S, Ojha AK, Patrice D, Yadav BS, Materny A (2016) One-step in situ synthesis of CeO2 nanoparticles grown on reduced graphene oxide as an excellent fluorescent and photocatalyst material under sunlight irradiation. Phys Chem Chem Phys 18(16):11157–11167. CrossRefGoogle Scholar
  20. Kurtikyan TS, Eksuzyan SR, Hayrapetyan VA, Martirosyan GG, Hovhannisyan GS, Goodwin GA (2012) Nitric oxide dioxygenation reaction by oxy-coboglobin models: in-situ low-temperature FTIR characterization of coordinated peroxynitrite. J Am Chem Soc 134(33):13861–13870. CrossRefGoogle Scholar
  21. Li JH, Shen B, Hong ZH, Lin BZ, Gao BF, Chen YL (2012) A facile approach to synthesize novel oxygen-doped g-C3N4 with superior visible-light photoreactivity. Chem Commun 48(98):12017–12019. CrossRefGoogle Scholar
  22. Lin B, An H, Yan X, Zhang T, Wei J, Yang G (2017) Fish-scale structured g-C3N4 nanosheet with unusual spatial electron transfer property for high-efficiency photocatalytic hydrogen evolution. Appl Catal B Environ 210:173–183. CrossRefGoogle Scholar
  23. Liu CY, Huang HW, Cui W, Dong F, Zhang YH (2018) Band structure engineering and efficient charge transport in oxygen substituted g-C3N4 for superior photocatalytic hydrogen evolution. Appl Catal B Environ 230:115–124. CrossRefGoogle Scholar
  24. Lorencik S, Yu QL, Brouwers HJH (2016) Photocatalytic coating for indoor air purification: synergetic effect of photocatalyst dosage and silica modification. Chem Eng J 306:942–952. CrossRefGoogle Scholar
  25. Ming LF, Yue H, Xu LM, Chen F (2014) Hydrothermal synthesis of oxidized g-C3N4 and its regulation of photocatalytic activity. J Mater Chem A 2(45):19145–19149. CrossRefGoogle Scholar
  26. Mo Z, Xu H, Chen ZG, She XJ, Song YH, Wu JJ, Yan PC, Xu L, Lei YC, Yuan SQ, Li HM (2018) Self-assembled synthesis of defect-engineered graphitic carbon nitride nanotubes for efficient conversion of solar energy. Appl Catal B Environ 225:154–161. CrossRefGoogle Scholar
  27. Pan L, Wang S, Xie J, Wang L, Zhang X, Zou JJ (2016) Constructing TiO2 pn homojunction for photoelectrochemical and photocatalytic hydrogen generation. Nano Energy 28:296–303. CrossRefGoogle Scholar
  28. Robert D, Keller N, Selli E (2017) Environmental photocatalysis and photochemistry for a sustainable world: a big challenge. Environ Sci Pollut Res 24(14):12503–12505. CrossRefGoogle Scholar
  29. Saadati F, Keramati N, Ghazi MM (2016) Influence of parameters on the photocatalytic degradation of tetracycline in wastewater: a review. Crit Rev Environ Sci Technol 46(8):757–782. CrossRefGoogle Scholar
  30. Shalom M, Inal S, Fettkenhauer C, Neher D, Antonietti M (2013) Improving carbon nitride photocatalysis by supramolecular preorganization of monomers. J Am Chem Soc 135(19):7118–7121. CrossRefGoogle Scholar
  31. She XJ, Wu JJ, Zhong J, Xu H, Yang YC, Vajtai R, Lou J, Liu Y, Du DL, Li HM, Ajayan PM (2016) Oxygenated monolayer carbon nitride for excellent photocatalytic hydrogen evolution and external quantum efficiency. Nano Energy 27:138–146. CrossRefGoogle Scholar
  32. Singh S, Lo SL (2018) Single-phase cerium oxide nanospheres: an efficient photocatalyst for the abatement of rhodamine B dye. Environ Sci Pollut Res 25(7):6532–6544. CrossRefGoogle Scholar
  33. Song YL, Qi JY, Tian JY, Gao SS, Cui FY (2018) Construction of Ag/g-C3N4 photocatalysts with visible-light photocatalytic activity for sulfamethoxazole degradation. Chem Eng J 341:547–555. CrossRefGoogle Scholar
  34. Teng F, Liu ZL, Zhang A (2015) Photocatalytic performances of Ag3PO4 polypods for degradation of dye pollutant under natural indoor weak light irradiation. Environ Sci Technol 49(16):9489–9494. CrossRefGoogle Scholar
  35. Thormählen I, Straub J, Grigull U (1985) Refractive index of water and its dependence on wavelength, temperature, and density. J Phys Chem Ref Data 14(4):933–945. CrossRefGoogle Scholar
  36. Tong Z, Yang D, Li Z, Nan Y, Ding F, Shen Y, Jiang Z (2017) Thylakoid-inspired multishell g-C3N4 nanocapsules with enhanced visible-light harvesting and electron transfer properties for high-efficiency photocatalysis. ACS Nano 11(1):1103–1112. CrossRefGoogle Scholar
  37. Wang XC, Maeda K, Thomas A, Takanabe K, Xin G, Carlsson JM, Domen K, Antonietti M (2009) A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat Mater 8(1):76–80. CrossRefGoogle Scholar
  38. Wang H, Yuan XZ, Wang H, Chen XH, Wu ZB, Jiang LB, Xiong WP, Zeng GM (2016) Facile synthesis of Sb2S3/ultrathin g-C3N4 sheets heterostructures embedded with g-C3N4 quantum dots with enhanced NIR-light photocatalytic performance. Appl Catal B Environ 193:36–46. CrossRefGoogle Scholar
  39. Wang YX, Wang H, Chen FY, Cao F, Zhao XH, Meng SG, Cui YJ (2017) Facile synthesis of oxygen doped carbon nitride hollow microsphere for photocatalysis. Appl Catal B Environ 206:417–425. CrossRefGoogle Scholar
  40. Wang H, Wu Y, Feng MB, Tu WG, Xiao T, Xiong T, Ang HX, Yuan XZ, Chew JW (2018a) Visible-light-driven removal of tetracycline antibiotics and reclamation of hydrogen energy from natural water matrices and wastewater by polymeric carbon nitride foam. Water Res 144:215–225. CrossRefGoogle Scholar
  41. Wang PF, Guo X, Rao L, Wang C, Guo Y, Zhang LX (2018b) A weak-light-responsive TiO2/g-C3N4 composite film: photocatalytic activity under low-intensity light irradiation. Environ Sci Pollut Res 25(20):20206–20216. CrossRefGoogle Scholar
  42. Wu YT, Yu YH, Nguyen VH, Lu KT, Wu JCS, Chang LM, Kuo CW (2013) Enhanced xylene removal by photocatalytic oxidation using fiber-illuminated honeycomb reactor at ppb level. J Hazard Mater 262(262C):717–725. CrossRefGoogle Scholar
  43. Wu JJ, Li N, Zhang XH, Fang HB, Zheng YZ, Tao X (2018a) Heteroatoms binary-doped hierarchical porous g-C3N4 nanobelts for remarkably enhanced visible-light-driven hydrogen evolution. Appl Catal B Environ 226:61–70. CrossRefGoogle Scholar
  44. Wu ZB, Yuan XZ, Zeng GM, Jiang LB, Zhong H, Xie YC, Wang H, Chen XH, Wang H (2018b) Highly efficient photocatalytic activity and mechanism of Yb3+/Tm3+ codoped In2S3 from ultraviolet to near infrared light towards chromium (VI) reduction and rhodamine B oxydative degradation. Appl Catal B Environ 225:8–21. CrossRefGoogle Scholar
  45. Yan J, Chen ZG, Ji HY, Liu Z, Wang X, Xu YG, She XJ, Huang LY, Xu L, Xu H, Li HM (2016) Construction of a 2D graphene-like MoS2/C3N4 heterojunction with enhanced visible-light photocatalytic activity and photoelectrochemical activity. Chemistry 22(14):4764–4773. CrossRefGoogle Scholar
  46. Ye LQ, Liu JY, Jiang Z, Peng TY, Zan L (2013) Facets coupling of BiOBr-g-C3N4 composite photocatalyst for enhanced visible-light-driven photocatalytic activity. Appl Catal B Environ 142–143:1–7. Google Scholar
  47. Yuan JL, Liu X, Tang YH, Zeng YX, Wang LL, Zhang SQ, Cai T, Liu YT, Luo SL, Pei Y, Liu CB (2018) Positioning cyanamide defects in g-C3N4: engineering energy levels and active sites for superior photocatalytic hydrogen evolution. Appl Cata B: Environ 237:24–31. CrossRefGoogle Scholar
  48. Zeng YX, Liu CB, Wang LL, Xu YZ, Liu YT, Luo SL (2016) A three-dimensional graphitic carbon nitride belt network for enhanced visible light photocatalytic hydrogen evolution. J Mater Chem A 4:19003–19010. CrossRefGoogle Scholar
  49. Zeng YX, Liu X, Liu CB, Wang LL, Xia YC, Zhang SQ, Luo SL, Pei Y (2018) Scalable one-step production of porous oxygen-doped g-C3N4 nanorods with effective electron separation for excellent visible-light photocatalytic activity. Appl Catal B Environ 224:1–9. CrossRefGoogle Scholar
  50. 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(1):18–21. CrossRefGoogle Scholar
  51. Zhang JS, Zhang MW, Yang C, Wang XC (2014) Nanospherical carbon nitride frameworks with sharp edges accelerating charge collection and separation at a soft photocatalytic interface. Adv Mater 26(24):4121–4126. CrossRefGoogle Scholar
  52. Zhang Z, Wang H, Wang X, Li YM, Song B, Bolarinwa O, Reese RA, Zhang T, Wang XQ, Cai JF, Xu BQ, Wang M, Liu CL, Yang HB, Li XP (2017) Supersnowflakes: stepwise self-assembly and dynamic exchange of rhombus star-shaped supramolecules. J Am Chem Soc 139(24):8174–8185. CrossRefGoogle Scholar
  53. Zhang J, Yuan XZ, Jiang LB, Wu ZB, Chen XH, Wang H, Wang H, Zeng GM (2018a) Highly efficient photocatalysis toward tetracycline of nitrogen doped carbon quantum dots sensitized Bi2WO6 based on interfacial charge transfer. J Colloid Interf Sci 511:296–306. CrossRefGoogle Scholar
  54. Zhang JW, Gong S, Mahmood N, Pan L, Zhang XW, Zou JJ (2018b) Oxygen-doped nanoporous carbon nitride via water-based homogeneous supramolecular assembly for photocatalytic hydrogen evolution. Appl Catal B Environ 221:9–16. CrossRefGoogle Scholar
  55. Zhao Y, Truhlar DG (2008) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Accounts 120(1–3):215–241. CrossRefGoogle Scholar
  56. Zheng D, Cao XN, Wang X (2016) Precise formation of a hollow carbon nitride structure with a Janus surface to promote water splitting by photoredox catalysis. Angew Chem Int Ed 55(38):11512–11516. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Key Laboratory of Integrated Regulation and Resource Development on Shallow Lakes, Ministry of Education, College of EnvironmentHohai UniversityNanjingChina
  2. 2.College of Mechanics and MaterialsHohai UniversityNanjingChina

Personalised recommendations