硼掺杂石墨相氮化碳的制备及其光催化降解水中有机污染物性能研究
Synthesis of Boron-Doped Graphitic Carbon Nitride and Its Photocatalytic Degradation of Organic Pollutants in Wastewater
摘要: 石墨相氮化碳(g-C3N4)作为一种极具潜力的非金属光催化剂，因其独特的电子结构和环境友好特性受到广泛关注。然而，纯g-C3N4存在光生载流子复合率高、比表面积有限等问题，限制了其实际应用。本研究以三聚氰胺为前驱体，通过热聚合法制备纯g-C3N4，并采用硼酸原位掺杂策略合成了一系列硼改性石墨相氮化碳催化剂(B-C3N4)。通过表征发现，硼掺杂保留了g-C3N4的基本骨架，但显著破坏了其层状堆叠结构，增强了光吸收和电荷分离效率。实验结果表明，B-C3N4对罗丹明B(RhB)、甲基橙(MO)和双酚A(BPA)等污染物的降解效率明显优于g-C3N4。此外，循环实验和自然光下降解测试表明B-C3N4具有良好的稳定性和实际应用潜力。该研究为开发高效、稳定的非金属光催化剂提供了新思路，在环境污染治理领域具有重要应用价值。
Abstract: Graphite-phase carbon nitride (g-C3N4), as a promising non-metallic photocatalyst, has attracted much attention due to its unique electronic structure and environmentally friendly properties. However, pure g-C3N4 suffers from high photogenerated carrier recombination rate and limited specific surface area, which limits its practical application. In this study, pure g-C3N4 was prepared by thermal polymerisation using melamine as a precursor and a series of boron-modified graphitic phase carbon nitride catalysts (B-C3N4) were synthesised using a in situ boron doping strategy. Characterisation reveals that boron doping preserves the basic skeleton of g-C3N4 but significantly disrupts its layered stacking structure, enhancing light absorption and charge separation efficiency. The experimental results showed that the degradation efficiency of B-C3N4 for pollutants such as Rhodamine B (RhB), Methyl Orange (MO) and Bisphenol A (BPA) was significantly better than that of g-C3N4. In addition, the cycling experiments and the degradation tests under natural light showed that B-C3N4 has good stability and potential for practical applications. This study provides a new idea for the development of highly efficient and stable non-metallic photocatalysts, which has important application value in the field of environmental pollution treatment.
文章引用：李紫尧, 孙旭镯, 李波. 硼掺杂石墨相氮化碳的制备及其光催化降解水中有机污染物性能研究[J]. 物理化学进展, 2025, 14(3): 542-551. https://doi.org/10.12677/japc.2025.143051

参考文献

[1] Fatima, M., Farooq, R., Lindström, R.W. and Saeed, M. (2017) A Review on Biocatalytic Decomposition of Azo Dyes and Electrons Recovery. Journal of Molecular Liquids, 246, 275-281. [Google Scholar] [CrossRef] 
[2] Liu, W., He, C., Zhu, B., Zhu, E., Zhang, Y., Chen, Y., et al. (2023) Progress in Wastewater Treatment via Organic Supramolecular Photocatalysts under Sunlight Irradiation. Chinese Journal of Catalysis, 53, 13-30. [Google Scholar] [CrossRef] 
[3] Quesada, H.B., Baptista, A.T.A., Cusioli, L.F., Seibert, D., de Oliveira Bezerra, C. and Bergamasco, R. (2019) Surface Water Pollution by Pharmaceuticals and an Alternative of Removal by Low-Cost Adsorbents: A Review. Chemosphere, 222, 766-780. [Google Scholar] [CrossRef] [PubMed]
[4] Varjani, S., Rakholiya, P., Shindhal, T., Shah, A.V. and Ngo, H.H. (2021) Trends in Dye Industry Effluent Treatment and Recovery of Value Added Products. Journal of Water Process Engineering, 39, Article ID: 101734. [Google Scholar] [CrossRef] 
[5] Hundessa, N.K., Hu, C., Kang, D., Chou, P., Ajebe, E.G., Lee, K., et al. (2024) Ultra-High Flux Loose Nanofiltration Membrane Based on Metal Organic Framework (CAU-10-H)/P84 Co-Polyimide for Dye/Salt Fractionation from Industrial Waste Water. Desalination, 586, Article ID: 117871. [Google Scholar] [CrossRef] 
[6] Kumari, H., Ranga, R., Chahal, S., Devi, S., et al. (2023) A Review on Photocatalysis Used for Wastewater Treatment: Dye Degradation. Water, Air, & Soil Pollution, 234, Article No. 349. [Google Scholar] [CrossRef] [PubMed]
[7] Liu, Q., Zhou, Y., Lu, J. and Zhou, Y. (2020) Novel Cyclodextrin-Based Adsorbents for Removing Pollutants from Wastewater: A Critical Review. Chemosphere, 241, Article ID: 125043. [Google Scholar] [CrossRef] [PubMed]
[8] Liao, Q., Rong, H., Zhao, M., Luo, H., Chu, Z. and Wang, R. (2022) Strong Adsorption Properties and Mechanism of Action with Regard to Tetracycline Adsorption of Double-Network Polyvinyl Alcohol-Copper Alginate Gel Beads. Journal of Hazardous Materials, 422, Article ID: 126863. [Google Scholar] [CrossRef] [PubMed]
[9] Li, X., Li, K., Wu, J., Li, B., Wang, W. and Tang, J. (2024) Facile Preparation of Sodium Alginate Gel Beads Enhanced by Polyamino-Modified 3D Carbon for Efficient Remediation of Organic Dyes in Wastewater. Separation and Purification Technology, 339, Article ID: 126637. [Google Scholar] [CrossRef] 
[10] Nadali Pishnamaz, H.M., Ranjbar, E. and Baghdadi, M. (2023) Application of Iron-Intercalated Graphite for Modification of Nickel Foam Cathode in Heterogeneous Electro-Fenton System: Bisphenol a Removal from Water at Neutral pH. Chemosphere, 339, Article ID: 139787. [Google Scholar] [CrossRef] [PubMed]
[11] Nechchadi, B., Naribi, Z., Salhi, A., El Krati, M. and Tahiri, S. (2025) Synthesis, Characterisation and Photocatalytic Properties of ZnO/Carbonaceous Gelatin-Based Aerogel Material for Dyes Degradation in Water. Water, Air, & Soil Pollution, 236, Article No. 495. [Google Scholar] [CrossRef] 
[12] Chen, X., Chen, C. and Zang, J. (2023) Bi2MoO6 Nanoflower-Like Microsphere Photocatalyst Modified by Boron Doped Carbon Quantum Dots: Improving the Photocatalytic Degradation Performance of BPA in All Directions. Journal of Alloys and Compounds, 962, Article ID: 171167. [Google Scholar] [CrossRef] 
[13] dos Santos, C.R., Rosa e Silva, G.O., Dias Araújo, A.A., Serafim, T.G., Drumond, G.P., dos Santos, V.L., et al. (2025) Granular Anaerobic Membrane Bioreactor Coupled Hybrid Forward Osmosis—Membrane Distillation Module for Organic Matter, Nutrient and Bisphenol a Removal: Integrated Assessment of Performance, Cost, Toxicity, and Risks. Chemical Engineering Journal, 504, Article ID: 158022. [Google Scholar] [CrossRef] 
[14] Yu, X., Su, H., Zou, J., Liu, Q., Wang, L. and Tang, H. (2022) Doping-Induced Metal-N Active Sites and Bandgap Engineering in Graphitic Carbon Nitride for Enhancing Photocatalytic H2 Evolution Performance. Chinese Journal of Catalysis, 43, 421-432. [Google Scholar] [CrossRef] 
[15] Yang, H., Sun, S., Yang, Q. and Cui, J. (2024) Supramolecular Self-Assembled Graphitic Carbon Nitride Catalyst: A Comprehensive Review on Design Principle, Synthesis Strategy, Functionalization and Application. Nano Materials Science. [Google Scholar] [CrossRef] 
[16] Han, E., Li, Y., Wang, Q., Huang, W., Luo, L., Hu, W., et al. (2019) Chlorine Doped Graphitic Carbon Nitride Nanorings as an Efficient Photoresponsive Catalyst for Water Oxidation and Organic Decomposition. Journal of Materials Science & Technology, 35, 2288-2296. [Google Scholar] [CrossRef] 
[17] Bellamkonda, S., Shanmugam, R. and Gangavarapu, R.R. (2019) Extending the π-Electron Conjugation in 2D Planar Graphitic Carbon Nitride: Efficient Charge Separation for Overall Water Splitting. Journal of Materials Chemistry A, 7, 3757-3771. [Google Scholar] [CrossRef] 
[18] Liu, T., Zhu, W., Wang, N., Zhang, K., Wen, X., Xing, Y., et al. (2023) Preparation of Structure Vacancy Defect Modified Diatomic‐Layered g-C3N4 Nanosheet with Enhanced Photocatalytic Performance. Advanced Science, 10, Article ID: 2302503. [Google Scholar] [CrossRef] [PubMed]
[19] Zhang, R., Bi, L., Wang, D., Lin, Y., Zou, X., Xie, T., et al. (2020) Investigation on Various Photo-Generated Carrier Transfer Processes of SnS2/g-C3N4 Heterojunction Photocatalysts for Hydrogen Evolution. Journal of Colloid and Interface Science, 578, 431-440. [Google Scholar] [CrossRef] [PubMed]
[20] Tsang, C.H.A., Li, K., Zeng, Y., Zhao, W., Zhang, T., Zhan, Y., et al. (2019) Titanium Oxide Based Photocatalytic Materials Development and Their Role of in the Air Pollutants Degradation: Overview and Forecast. Environment International, 125, 200-228. [Google Scholar] [CrossRef] [PubMed]
[21] Gao, M., Feng, J., Zhang, Z., Gu, M., Wang, J., Zeng, W., et al. (2018) Wrinkled Ultrathin Graphitic C3N4 Nanosheets for Photocatalytic Degradation of Organic Wastewater. ACS Applied Nano Materials, 1, 6733-6741. [Google Scholar] [CrossRef] 
[22] Yang, H., Zhang, A., Ding, J., Hu, R., Gong, Y., Li, X., et al. (2024) Amino Modulation on the Surface of Graphitic Carbon Nitride for Enhanced Photocatalytic Hydrogen Production. Carbon, 219, Article ID: 118841. [Google Scholar] [CrossRef] 
[23] Yang, Y., Mao, B., Gong, G., Li, D., Liu, Y., Cao, W., et al. (2019) In-Situ Growth of Zn-AgIn5S8 Quantum Dots on g-C3N4 towards 0D/2D Heterostructured Photocatalysts with Enhanced Hydrogen Production. International Journal of Hydrogen Energy, 44, 15882-15891. [Google Scholar] [CrossRef] 
[24] Zhang, C., Qin, D., Zhou, Y., Qin, F., Wang, H., Wang, W., et al. (2022) Dual Optimization Approach to Mo Single Atom Dispersed g-C3N4 Photocatalyst: Morphology and Defect Evolution. Applied Catalysis B: Environmental, 303, Article ID: 120904. [Google Scholar] [CrossRef] 
[25] Wei, Q., Zhang, A., Yang, Z., Hu, S., Wang, D., Zhang, C., et al. (2023) Oxygen-Exfoliated Cobalt-Doped C3N4 for Superior Fenton-Like Catalysis: The Accessible Metal Exposure and Synergistic Pollutant Adsorption from Three-Dimensional Layered Configuration. Journal of Environmental Chemical Engineering, 11, Article ID: 111067. [Google Scholar] [CrossRef] 
[26] Peng, Q., Ye, L., Wen, N., Chen, H., Zhu, Y., Niu, H., et al. (2025) Nitrogen Vacancy-Modified g-C3N4 Nanosheets Controlled by Deep Eutectic Solvents for Highly Efficient Photocatalytic Atrazine Degradation: Non-Radical Dominated Holes Oxidation. Separation and Purification Technology, 354, Article ID: 128879. [Google Scholar] [CrossRef] 
[27] Zhao, X., Liu, X., Yi, C., Li, J., Su, Y. and Guo, M. (2020) Palladium Nanoparticles Embedded in Yolk-Shell N-Doped Carbon Nanosphere@Void@SnO2 Composite Nanoparticles for the Photocatalytic Reduction of 4-Nitrophenol. ACS Applied Nano Materials, 3, 6574-6583. [Google Scholar] [CrossRef] 
[28] Ullah, R., Rafiq, M., Alamgir, Qadir, A., Ahmed, A., Fayaz, M., et al. (2025) Hollow Cavity Engineering of MOF-Derived Hierarchical Nitrogen-Doped In2O3@carbon for Efficient Photocatalytic Degradation of Tetracycline Hydrochloride. Journal of Water Process Engineering, 76, Article ID: 108311. [Google Scholar] [CrossRef]