طراحی فوتوکاتالیست‌های چندمنظوره با g-C₃N₄ و کاربردهای آن در فناوری‌های پایدار

محورهای موضوعی : راه حل های موثر و قابل توسعه برای کنترل و حذف آلودگی های محیطی

زهرا محمدپور کوسه لر ¹ , زهره قاضی طباطبایی ^{2 *}

1 - دانشجوی کارشناسی ارشد، گروه شیمی، واحد اهر، دانشگاه آزاد اسلامی، اهر، ایران
2 - استادیار گروه شیمی، واحد اهر، دانشگاه آزاد اسلامی، اهر، ایران

تاریخ دریافت : 1403/09/08 تاریخ پذیرش : 1403/09/19 تاریخ انتشار : 1403/10/18

کلید واژه: نیترید کربن گرافیتی, فوتوکاتالیست‌ ناهمگن, فناوری‌های پایدار, طراحی فوتوکاتالیست‌ ,

چکیده مقاله :

فوتوکاتالیست­های ناهمگن در تبدیل و ذخیره انرژی، در سوخت‌های خورشیدی پایدار و سبز و همچنین در بسیاری از حوزه‌های زیست‌محیطی به‌عنوان یک فناوری نوین به‌کار می‌روند. فوتوکاتالیست­های نیترید کربن گرافیتی (g-C₃N₄) به دلیل ویژگی‌های فیزیکوشیمیایی، نوری و الکتریکی منحصر به فرد خود، طیف خاصی از فوتوکاتالیست­های ناهمگن را تشکیل می­دهند. در این مطالعه، مکانیسم‌های اصلی این فوتوکاتالیست‌ها، مزایا، چالش‌ها و طراحی فوتوکاتالیست‌های مبتنی بر g-C₃N₄  مورد بررسی قرار گرفت. همچنین، خواص ساختاری، ویژگی­های فیزیکوشیمیایی سطح، پایداری سطح، هم­چنین خواص الکتروشیمیایی، فوتوالکتروشیمیایی و نوری آن­ها به تفصیل بررسی شد. همچنین، کاربردهای مهمی نظیر تخریب آلاینده­ها، کاهش دی‌اکسید کربن، برخی تبدیلات آلی و گندزدایی نیز مورد توجه قرار گرفت. با توجه به پیشرفت‌های برجسته این حوزه، انتظار می‌رود که فرصت‌های جدیدی برای طراحی و ساخت فوتوکاتالیست‌های موثر مبتنی بر g-C₃N₄ برای کاربردهای مختلف فراهم شود.   

چکیده انگلیسی:

Heterogeneous photocatalysts are utilized as a novel technology in energy conversion and storage, particularly in sustainable and green solar fuels, as well as in a variety of environmental applications. Graphitic carbon nitride (g-C₃N₄) photocatalysts form a specific group of heterogeneous photocatalysts due to their unique physicochemical, optical, and electrical properties. In this review, the fundamental mechanisms of heterogeneous photocatalysts, their advantages, challenges, and the design of g-C₃N₄-based photocatalysts are examined. The structural properties, surface physicochemical characteristics, surface stability, as well as their electrochemical, photoelectrochemical, and optical properties are highlighted. Key applications, such as pollutant degradation, carbon dioxide reduction, certain organic transformations, and disinfection, are also addressed. By reviewing significant advancements in this field, new opportunities for the design and fabrication of highly efficient g-C₃N₄-based photocatalysts for diverse applications are expected to arise.

منابع و مأخذ:

[1] Fujishima, A, Honda, K., 1972, Electrochemical photolysis of water at a semiconductor electrode, Nature, 238, 37.
[2] Bard, A.J., 1979, Photoelectrochemistry and heterogeneous photo-catalysis at semiconductors, Journal of Photochemistry, 10, 59.
[3] Kato, H., Hori, M., Konta, R., Shimodaira, Y., Kudo, A., 2004, Construction of Z-scheme type heterogeneous photocatalysis systems for water splitting into H2 and O2 under visible light irradiation, Chemistry Letters, 33, 1348.
[4] Wang, C.-C., Li, J.-R., Lv, X.-L., Zhang, Y.-Q., Guo, G., 2014, Photocatalytic organic pollutants degradation in metal-organic frameworks, Energy & Environmental Science, 7, 2831.
[5] Li, X., Wen, J., Low, J., Fang, Y., Yu, J., 2014, Design and fabrication of semiconductor photocatalyst for photocatalytic reduction of CO2 to solar fuel, Science China Materials, 57, 70.
[6] Lang, X., Chen, X., Zhao, J., 2014, Heterogeneous visible light photocatalysis for selective organic transformations, Chemical Society Reviews, 43, 473.
[7] Masih, D., Ma, Y,. Rohani, S., 2017, Graphitic C3N4 based noble-metal-free photocatalyst systems: A review, Applied Catalysis B: Environmental, 206, 556.
[8] Patnaik, S., Sahoo, D.P., Parida, K., 2018, An overview on Ag modified g-C3N4 based nanostructured materials for energy and environmental applications, Renewable and Sustainable Energy Reviews, 82, 1297.
[9] Ran, J., Gao, G., Li, F.-T., Ma, T.-Y., Du, A., Qiao, S.-Z., 2017, Ti3C2 MXene co-catalyst on metal sulfide photo-absorbers for enhanced visible-light photocatalytic hydrogen production, Nature Communications, 8, 13907.
[10] Kumar, S., Karthikeyan, S., Lee, A.F., 2018, g-C3N4-based nanomaterials for visible light-driven photocatalysis, Catalysts, 8, 74.
[11] Chen, F., Yang, H., Wang, X., Yu, H., 2017, Facile synthesis and enhanced photocatalytic H2-evolution performance of NiS2-modified g-C3N4 photocatalysts, Chinese Journal of Catalysis, 38, 296.
[12] Cao, S., Huang, Q., Zhu, B., Yu, J., 2017, Trace-level phosphorus and sodium co-doping of g-C3N4 for enhanced photocatalytic H2 production, Journal of Power Sources, 351, 151.
[13] Gomari, K.A., Hafeez, H.Y., Mohammed, J., Dankawu, U.M., Ndikilar, C.E., Suleiman, A.B., 2024, A recent development and future prospect of g–C3N4–based photocatalyst for stable hydrogen (H2) generation via photocatalytic water-splitting, International Journal of Hydrogen Energy, 85, 598.
[14] Hao, P., Chen, Z., Yan, Y., Shi, W., Guo, F., 2024, Recent advances, application and prospect in g-C3N4-based S-scheme heterojunction photocatalysts, Separation and Purification Technology, 330, 125302.
[15] Li, Y., Zhou, M., Cheng, B., Shao, Y., 2020, Recent advances in g-C3N4-based heterojunction photocatalysts, Journal of Materials Science & Technology, 56, 1.
[16] Yang, X., Ye, Y., Sun, J., Li, Z., Ping, J., Sun, X., 2022, Recent advances in g-C3N4‐based photocatalysts for pollutant degradation and bacterial disinfection: Design strategies, mechanisms, and applications, Small, 18, 2105089.
[17] Xing, J., Wang, N., Li, X., Wang, J., Taiwaikuli, M., Huang, X., Wang, T., Zhou, L. Hao, H., 2022, Synthesis and modifications of g-C3N4-based materials and their applications in wastewater pollutants removal, Journal of Environmental Chemical Engineering, 10, 108782.
[18] Sohail, M., Anwar, U., Taha, T.A., Qazi, H.I.A., Al-Sehemi, A.G., Ullah, S., Algarni, H., Ahmed, I.M., Amin, M.A., Palamanit, A. Iqbal, W., Alharthi, S., Nawawi, W.I., Ajmal, Z., Ali, H., Hayat, A., 2022, Nanostructured materials based on g-C3N4 for enhanced photocatalytic activity and potentials application: A review, Arabian Journal of Chemistry, 15, 104070.
[19] Yan, Y., Meng, Q., Tian, L., Cai, Y., Zhang, Y. Chen, Y., 2024, Engineering of g-C3N4 for photocatalytic hydrogen production: A review, International Journal of Molecular Sciences, 25, 8842.
[20] Ismael, M., 2020, A review on graphitic carbon nitride (g-C3N4) based nanocomposites: Synthesis, categories, and their application in photocatalysis, Journal of Alloys and Compounds, 846, 156446.
[21] He, F., Wang, Z., Li, Y., Peng, S., Liu, B., 2020, The nonmetal modulation of composition and morphology of g-C3N4-based photocatalysts, Applied Catalysis B: Environmental, 269, 118828.
[22] Hayat, A., Sohail, M., El Jery, A., Al‐Zaydi, K.M., Alshammari, K.F., Khan, J., Ali, H., Ajmal, Z., Taha, T.A., Ud Din, I., Altamimi, R., Hussein, M.A., Al-Hadeethi, Y., Orooji, Y., Ansari, M.Z., 2023, Different dimensionalities, morphological advancements and engineering of g-C3N4‐based nanomaterials for energy conversion and storage, The Chemical Record, 23, e202200171.
[23] Song, B., Zeng, Z., Zeng, G., Gong, J., Xiao, R., Ye, S., Chen, M., Lai, C., Xu, P., Tang, X., 2019, Powerful combination of g-C3N4 and LDHs for enhanced photocatalytic performance: A review of strategy, synthesis, and applications, Advances in Colloid and Interface Science, 272, 101999.
[24] Wudil, Y.S., Ahmad, U.F., Gondal, M.A., Al-Osta, M.A., Almohammedi, A., Sa'id, R.S., Hrahsheh, F., Haruna, K., Mohamed, M.J.S., 2023, Tuning of graphitic carbon nitride (g-C3N4) for photocatalysis: A critical review, Arabian Journal of Chemistry, 16, 104542.
[25] Wang, J., Wang, S., 2022, A critical review on graphitic carbon nitride (g-C3N4)-based materials: Preparation, modification and environmental application, Coordination Chemistry Reviews, 453, 214338.
[26] Li, Y., Gu, M., Zhang, X., Fan, J., Lv, K., Carabineiro, S.A.C., Dong, F., 2020, 2D g-C3N4 for advancement of photo-generated carrier dynamics: Status and challenges, Materials Today, 41, 270.
[27] Huang, H., Jiang, L., Yang, J., Zhou, S., Yuan, X., Liang, J., Wang, H., Wang, H., Bu, Y., Li, H., 2023, Synthesis and modification of ultrathin g-C3N4 for photocatalytic energy and environmental applications, Renewable and Sustainable Energy Reviews, 173, 113110.
[28] Khan, M.A., Mutahir, S., Shaheen, I., Qunhui, Y., Bououdina, M., Humayun, M., 2025, Recent advances over the doped g-C3N4 in photocatalysis: A review, Coordination Chemistry Reviews, 522, 216227.
[29] Gorai, D.K., Kuila, S.K., Kumar, A., Ahmad, M.I., Kundu, T.K., 2023, Insight into the effect of Li/P co-doping on the electronic structure and photocatalytic performance of g-C3N4 by the first principle, Applied Surface Science, 623, 157031.
[30] Liu, X., Kang, W., Zeng, W., Zhang, Y., Qi, L., Ling, F., Fang, L., Chen, Q., Zhou, M., 2020, Structural, electronic and photocatalytic properties of g-C3N4 with intrinsic defects: A first-principles hybrid functional investigation, Applied Surface Science, 499, 143994.
[31] Liu, J., Cheng, B., 2018, New understanding of photocatalytic properties of zigzag and armchair g-C3N4 nanotubes from electronic structures and carrier effective mass, Applied Surface Science, 430, 348.
[32] Xu, Q., Ma, D., Yang, S., Tian, Z., Cheng, B., Fan, J., 2019, Novel g-C3N4/g-C3N4 S-scheme isotype heterojunction for improved photocatalytic hydrogen generation, Applied Surface Science, 495,143555.
[33] Li, Y., Yang, M., Xing, Y., Liu, X., Yang, Y., Wang, X., Song, S., 2017, Preparation of carbon‐rich g-C3N4 nanosheets with enhanced visible light utilization for efficient photocatalytic hydrogen production, Small, 13, 1701552.
[34] Bandyopadhyay, A., Ghosh, D., Kaley, N.M., Pati, S.K., 2017, Photocatalytic activity of g-C3N4 quantum dots in visible light: Effect of physicochemical modifications, The Journal of Physical Chemistry C, 121, 1982.
[35] Dong, S., Cai, W., Sheng, L., Wang, W., Liu, H., Xia, J., 2020, Combined effect of physicochemical factors on the retention and transport of g-C3N4 in porous media, Chemosphere, 256, 127100.
[36] Dong, G., Zhang, Y., Pan, Q., Qiu, J., 2014, A fantastic graphitic carbon nitride (g-C3N4) material: Electronic structure, photocatalytic and photoelectronic properties, Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 20, 33.
[37] Pomilla, F.R., Cortes, M.A.L.R.M., Hamilton, J.W.J., Molinari, R., Barbieri, G., Marcì, G., Palmisano, L., Sharma, P.K., Brown, A., Byrne, J.A., 2018, An Investigation into the stability of graphitic C3N4 as a photocatalyst for CO2 reduction, The Journal of Physical Chemistry C, 122, 28727.
[38] Pawar, R.C., Kang, S., Park, J.H., Kim, J.-H., Ahn, S., Lee, C.S., 2016, Room-temperature synthesis of nanoporous 1D microrods of graphitic carbon nitride (g-C3N4) with highly enhanced photocatalytic activity and stability, Scientific Reports, 6, 31147.
[39] Cherkasov, N., Ibhadon, A.O., Fitzpatrick, P., 2015, A review of the existing and alternative methods for greener nitrogen fixation, Chemical Engineering and Processing: Process Intensification, 90, 24.
[40] Ling, G.Z.S., Ng, S.-F., Ong, W.-J., 2022, Tailor‐engineered 2D cocatalysts: harnessing electron–hole redox center of 2D g-C3N4 photocatalysts toward solar‐to‐chemical conversion and environmental purification, Advanced Functional Materials, 32, 2111875.
[41] Tahir, M., Cao, C., Mahmood, N., Butt, F.K., Mahmood, A., Idrees, F., Hussain, S., Tanveer, M., Ali, Z., Aslam, I., 2014, Multifunctional g-C3N4 nanofibers: A template-free fabrication and enhanced optical, electrochemical, and photocatalyst properties, ACS Applied Materials & Interfaces, 6, 1258.
[42] Zhou, X., Zhao, C., Chen, J., Chen, L., 2021, Influence of B, Zn, and B-Zn doping on electronic structure and optical properties of g-C3N4 photocatalyst: A first-principles study, Results in Physics, 26, 104338.
[43] Zhang, H., Tang, Y., Liu, Z., Zhu, Z., Tang, X., Wang, Y., 2020, Study on optical properties of alkali metal doped g-C3N4 and their photocatalytic activity for reduction of CO2, Chemical Physics Letters, 751, 137467.
[44] Li, J., Liu, Y., Li, H., Chen, C., 2016, Fabrication of g-C3N4/TiO2 composite photocatalyst with extended absorption wavelength range and enhanced photocatalytic performance, Journal of Photochemistry and Photobiology A: Chemistry, 317, 151.
[45] Zhao, S., Chen, S., Yu, H., Quan, X., 2012, g-C3N4/TiO2 hybrid photocatalyst with wide absorption wavelength range and effective photogenerated charge separation, Separation and Purification Technology, 99, 50.
[46] Pan, Y., Zhang, Y., Li, Z., Yang, N., Deng, W., Fang, Z., Li, C., Long, Z., 2020, A selective cataluminescence sensor with a homemade gaseous sample introduction system for accurate and sensitive determination of H2S using catalytic g-C3N4@Fe, Microchemical Journal, 156, 104833.
[47] Ansari, S.A., Cho, M.H., 2017, Simple and large scale construction of MoS2-g-C3N4 heterostructures using mechanochemistry for high performance electrochemical supercapacitor and visible light photocatalytic applications, Scientific Reports, 7, 43055.
[48] Bu, Y., Chen, Z., Li, W., 2014, Using electrochemical methods to study the promotion mechanism of the photoelectric conversion performance of Ag-modified mesoporous g-C3N4 heterojunction material, Applied Catalysis B: Environmental, 144, 622.
[49] Nguyen-Dinh, M.-T., Bui, T.S., Bansal, P., Jourshabani, M., Lee, B.K., 2021, Photocatalytic and photo-electrochemical behavior of novel SnO2-modified-g-C3N4 for complete elimination of tetracycline under visible-light irradiation: Slurry and fixed-bed approach, Separation and Purification Technology, 267, 118607.
[50] Yu, X., He, X., Zhang, X., Peng, Y., Zhao, P., Zhang, Z., Liu, Y., Zhang, L., Zhao, P., 2024, Effect of P and Ce co-doping on the photocatalytic performance of g-C3N4: Experimental and theoretical studies, Diamond and Related Materials, 143, 110906.
[51] Liu, E., Lin, X., Hong, Y., Yang, L., Luo, B., Shi, W., Shi, J., 2021, Rational copolymerization strategy engineered C self-doped g-C3N4 for efficient and robust solar photocatalytic H2 evolution, Renewable Energy, 178, 757.
[52] Zou, H., Yan, X., Ren, J., Wu, X., Dai, Y., Sha, D., Pan, J., Liu, J., 2015, Photocatalytic activity enhancement of modified g-C3N4 by ionothermal copolymerization, Journal of Materiomics, 1, 340.
[53] Tong, Z., Yang, D., Shi, J., Nan, Y., Sun, Y., Jiang, Z., 2015, Three-dimensional porous aerogel constructed by g-C3N4 and graphene oxide nanosheets with excellent visible-light photocatalytic performance, ACS Applied Materials & Interfaces, 7, 25693.
[54] Mo, Z., Zhu, X., Jiang, Z., Song, Y., Liu, D., Li, H., Yang, X., She, Y., Lei, Y., Yuan, S., Li, H., Song, L., Yan, Q., Xu, H., 2019, Porous nitrogen-rich g-C3N4 nanotubes for efficient photocatalytic CO2 reduction, Applied Catalysis B: Environmental, 256, 117854.
[55] Zhou, X., Jin, B., Chen, R., Peng, F., Fang, Y., 2013, Synthesis of porous Fe3O4/g-C3N4 nanospheres as highly efficient and recyclable photocatalysts, Materials Research Bulletin, 48, 1447.
[56] Fattahimoghaddam, H., Mahvelati-Shamsabadi, T., Lee, B.-K., 2021, Efficient photodegradation of Rhodamine B and tetracycline over robust and green g-C3N4 nanostructures: Supramolecular design, Journal of Hazardous Materials, 403, 123703.
[57] Chen, Y., Zhai, B., Liang, Y., Li, Y., Li, J., 2019, Preparation of CdS/g-C3N4/MOF composite with enhanced visible-light photocatalytic activity for dye degradation, Journal of Solid State Chemistry, 274, 32.
[58] Balakrishnan, A., Chinthala, M., Polagani, R.K., Vo, D.-V.N., 2023, Removal of tetracycline from wastewater using g-C3N4 based photocatalysts: A review, Environmental Research, 216, 114660.
[59] Yuan, Q., Li, L., Tang, Y., Zhang, X., 2020, A facile Pt-doped g-C3N4 photocatalytic biosensor for visual detection of superoxide dismutase in serum samples, Sensors and Actuators B: Chemical, 318, 128238.
[60] Çapar, N., Yola, B.B., Polat, İ., Bekerecioğlu, S., Atar, N., Yola, M.L., 2023, A zearalenone detection based on molecularly imprinted surface plasmon resonance sensor including sulfur-doped g-C3N4/Bi2S3 nanocomposite, Microchemical Journal, 193, 109141.
[61] Xiong, T., Cen, W., Zhang, Y., Dong, F., 2016, Bridging the g-C3N4 interlayers for enhanced photocatalysis, ACS Catalysis, 6, 2462.
[62] Niu, X., Yi, Y., Bai, X., Zhang, J., Zhou, Z., Chu, L., Yang, J., Li, X., 2019, Photocatalytic performance of few-layer graphitic C3N4: Enhanced by interlayer coupling, Nanoscale, 11, 4101.
[63] Mohini, R., Lakshminarasimhan, N., 2016, Coupled semiconductor nanocomposite g-C3N4/TiO2 with enhanced visible light photocatalytic activity, Materials Research Bulletin, 76, 370.
[64] Pestana, C.J., Hui, J., Camacho-Muñoz, D., Edwards, C., Robertson, P.K.J., Irvine, J.T.S., Lawton, L.A., 2023, Solar-driven semi-conductor photocatalytic water treatment (TiO2, g-C3N4, and TiO2+g-C3N4) of cyanotoxins: Proof-of-concept study with microcystin-LR, Chemosphere, 310, 136828.
[65] Duan, C., Meng, X., Liu, C., Lu, W., Liu, J., Dai, L., Wang, W., Zhao, W., Xiong, C., Ni, Y., 2019, Carbohydrates-rich corncobs supported metal-organic frameworks as versatile biosorbents for dye removal and microbial inactivation, Carbohydrate Polymers, 222, 115042.