تهیه و مشخصه‌یابی نانوصفحات g−C3N4 دوپ‌شده با گوگرد به‌منظور افزایش فعالیت فوتوکاتالیستی در حذف آلاینده‌های آلی

نوع مقاله : مقاله پژوهشی

نویسندگان

دانشکده مهندسی شیمی و مواد، مجتمع آموزش عالی فنی و مهندسی اسفراین، اسفراین، خراسان شمالی، ایران

چکیده

مقدمه و اهداف: نیترید کربن گرافیتی (g−C3N4)، نیمه‌رسانایی امیدبخش برای فوتوکاتالیست‌ها است، اما کارایی آن به‌دلیل بازترکیب سریع حامل‌های بار و جذب ضعیف نور مرئی محدود می‌شود. این پژوهش، با هدف افزایش خواص فوتوکاتالیستی g−C3N4 ازطریق دوپ‌شدن گوگرد برای تخریب متیلن بلو تحت تابش نور مرئی انجام شد.
مواد و روش‌ها: نانوورقه‌های g−C3N4 با لایه‌برداری حرارتی ملامین سنتز و سپس با گوگرد دوپ شدند. به‌منظور بررسی موفقیت‌آمیز بودن فرآیند دوپ‌شدن و حفظ ساختار نانوورقه‌ها، مجموعه‌ای از آزمون‌های مشخصه‌یابی شامل پراش پرتو ایکس، میکروسکوپ الکترونی عبوری، طیف‌سنجی بازتابی انتشار یافته فرابنفش-مرئی و طیف‌سنجی پراش انرژی اشعه ایکس انجام گرفت.
نتایج: نمونه بهینه دوپ‌شده با گوگرد (S-CN-1.5)، عملکرد فوتوکاتالیستی بسیار بهتری نسبت‌به g−C3N4 خالص نشان داد. این نمونه تقریبا 95 درصد متیلن بلو را در 160 دقیقه تخریب کرد، درحالی‌که g−C3N4 خالص، تنها حدود 70 درصد تخریب داشت. این افزایش کارایی، به کاهش گاف نواری از 2/75 به 2/47 الکترون‌ولت نسبت داده می‌شود که منجر به افزایش جذب نور مرئی شد.
نتیجه‌گیری: دوپ‌شدن g−C3N4 با گوگرد، روشی مؤثر برای تقویت عملکرد فوتوکاتالیستی آن در تخریب آلاینده‌ها است. این رویکرد، توسعه مواد کارآمدتر و سازگار با محیط زیست را برای کاربردهای زیست‌محیطی هموار می‌کند.

کلیدواژه‌ها

موضوعات

عنوان مقاله [English]

Synthesis and Characterization of Sulfur-Doped g-C₃N₄ Nanosheets for Enhanced Photocatalytic Activity in The Removal of Organic Pollutants

نویسندگان [English]

  • Morteza Hajizadeh-Oghaz
  • Gholamreza Heidari
Department of Chemical and Materials Engineering, Esfarayen University of Technology, Esfarayen, North Khorasan, Iran
چکیده [English]

Introduction and Objectives: Graphitic carbon nitride (g−C3N4) is a promising metal-free semiconductor for photocatalytic applications. However, its efficiency is often limited by rapid charge carrier recombination and relatively low visible light absorption. This research aimed to significantly enhance the photocatalytic properties of g−C3N4 through sulfur doping, specifically for the degradation of the organic dye, methylene blue.
Materials and Methods: g−C3N4 nanosheets were synthesized via the thermal exfoliation of melamine. To assess the successful doping process and the preservation of the nanosheet structure, a set of characterization techniques, including X-ray diffraction, transmission electron microscopy, ultraviolet–visible diffuse reflectance spectroscopy, and energy dispersive spectroscopy, was employed.
Results: The optimized sulfur-doped sample (S-CN-1.5) exhibited significantly superior performance compared to the pure g−C3N4. This sample degraded approximately 95% of methylene blue within 160 minutes under visible light irradiation, whereas pure g−C3N4 achieved only about 70% degradation in the same period. This enhanced efficiency is attributed to the reduction in band gap from 2.75 eV for pure g−C3N4 to 2.47 eV for S-CN-1.5, which led to increased visible light absorption.
Conclusion: Overall, sulfur doping of g−C3N4 is an effective strategy to boost its photocatalytic performance in pollutant degradation. This approach paves the way for developing more efficient and environmentally friendly materials for various environmental applications.

کلیدواژه‌ها [English]

  • Graphitic carbon nitride
  • Sulfur doping
  • Photocatalyst
  • Nanosheets
  • Degradation of organic pollutants

مراجع

  1. Rizwan M, Zada A, Azizi S, Fazil P, Naeem M, Murtaza G, et al. Role of metal and non-metal dopants in modulating g-C3N4 for photocatalytic applications. Int J Hydrog Energy. 2025;97:1126–52. https://doi.org/10.1016/j.ijhydene.2024.11.397
  2. Ismael M. A review on graphitic carbon nitride (g-C3N4) based nanocomposites: Synthesis, categories, and their application in photocatalysis. J Alloys Compd. 2020;846:156446. https://doi.org/10.1016/j.jallcom.2020.156446
  3. Ong WJ, Tan LL, Ng YH, Yong ST, Chai SP. Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability? Chem Rev. 2016;116(12):7159–329. https://doi.org/10.1021/acs.chemrev.6b00075
  4. Jafari A, Khademi S, Farahmandjou M, Darudi A, Rasuli R. Preparation and Characterization of Cerium Doped Titanium Dioxide Nanoparticles by the Electrical Discharge Method. J Adv Mater Eng. 2019;38(2):83–90. https://doi.org/29252/jame.38.2.83
  5. Molaei MJ. Graphitic carbon nitride (g-C3N4) synthesis and heterostructures, principles, mechanisms, and recent advances: A critical review. Int J Hydrog Energy. 2023;48(84):32708–28. https://doi.org/10.1016/j.ijhydene.2023.05.066
  6. Hayat A, Al-Sehemi AG, El-Nasser KS, Taha TA, Al-Ghamdi AA, Jawad Ali Shah Syed, et al. Graphitic carbon nitride (g–C3N4)–based semiconductor as a beneficial candidate in photocatalysis diversity. Int J Hydrog Energy. 2022;47(8):5142–91. https://doi.org/10.1016/j.ijhydene.2021.11.133
  7. Niu P, Zhang L, Liu G, Cheng H. Graphene‐Like Carbon Nitride Nanosheets for Improved Photocatalytic Activities. Adv Funct Mater. 2012;22(22):4763–70. https://doi.org/10.1002/adfm.201200922
  8. Bai X, Yan S, Wang J, Wang L, Jiang W, Wu S, et al. A simple and efficient strategy for the synthesis of a chemically tailored g-C 3 N 4 J Mater Chem A 2014;2(41):17521–9. https://doi.org/10.1039/C4TA02781G
  9. Pérez-Torres AF, Hernández-Barreto DF, Bernal V, Giraldo L, Moreno-Piraján JC, Da Silva EA, et al. Sulfur-Doped g-C3 N4 Heterojunctions for Efficient Visible Light Degradation of Methylene Blue. ACS Omega 2023;8(50):47821–34. https://doi.org/10.1021/acsomega.3c06320
  10. Xing J, Wang N, Li X, Wang J, Taiwaikuli M, Huang X, et al. Synthesis and modifications of g-C3N4-based materials and their applications in wastewater pollutants removal. J Environ Chem Eng. 2022;10(6):108782. https://doi.org/10.1016/j.jece.2022.108782
  11. Guan K, Li J, Lei W, Wang H, Tong Z, Jia Q, et al. Synthesis of sulfur doped g-C3N4 with enhanced photocatalytic activity in molten salt. J Materiomics. 2021;7(5):1131–42. https://doi.org/10.1016/j.jmat.2021.01.008
  12. An TD, Phuc NV, Tri NN, Phu HT, Hung NP, Vo V. Sulfur-Doped g-C3N4 with Enhanced Visible-Light Photocatalytic Activity. Appl Mech Mater. 2019;889: 43–50. https://doi.org/10.4028/www.scientific.net/AMM.889.43
  13. Kianipour S, Razavi FS, Hajizadeh-Oghaz M, Abdulsahib WK, Mahdi MA, Jasim LS, et al. The synthesis of the P/N-type NdCoO3/g-C3N4 nano-heterojunction as a high-performance photocatalyst for the enhanced photocatalytic degradation of pollutants under visible-light irradiation. Arab J Chem. 2022;15(6):103840. https://doi.org/10.1016/j.arabjc.2022.103840
  14. Fei Y, Han N, Zhang M, Yang F, Yu X, Shi L, et al. Facile preparation of visible light-sensitive layered g-C3N4 for photocatalytic removal of organic pollutants. Chemosphere. 2022;307:135718. https://doi.org/10.1016/j.chemosphere.2022.135718
  15. Yang Y, Chen J, Mao Z, An N, Wang D, Fahlman BD. Ultrathin g-C 3 N 4 nanosheets with an extended visible-light-responsive range for significant enhancement of photocatalysis. RSC Adv. 2017;7(4):2333–41. https://doi.org/10.1039/C6RA26172H
  16. Abbas S, Khurshid H, Irfan M, Aamir M. Characterisation Analysis of Sulphur and Phosphorous Doped and Co-doped Graphitic Carbon Nitride (g-C₃N₄) Materials. Lond J Phys. 2024;1(2). https://doi.org/10.69710/ljp.v1i2.10365
  17. Sylvia B, Sumy J, Vishnu Kamath P. Distinguishing crystallite size effects from those of structural disorder on the powder X-ray diffraction patterns of layered materials | Journal of Chemical Sciences. J Chem Sci 2010;122(5):751-756. https://doi.org/10.1007/s12039-010-0063-2
  18. Shcherban ND, Filonenko SM, Ovcharov ML, Mishura AM, Skoryk MA, Aho A, Murzin DY. Simple method for preparing of sulfur–doped graphitic carbon nitride with superior activity in CO2 chemistryselect 2016;1:4987–4993. https://doi.org/10.1002/slct.201601283
  19. Kharatzadeh E, Khademalrasool M. Synthesis of S-doped g-C3N4 nanostructures by reflux method and study of photocatalytic and photoelectrochemical performances. Ceram Int. 2024;50(9, Part B):16540–52. https://doi.org/10.1016/j.ceramint.2024.02.144
  20. Sergey S, Sebastian Z. Sulfur doping effects on the electronic and geometric structures of graphitic carbon nitride photocatalyst: insights from first principles. J Phys Condens Matter. 2013;25(8):085507. https://doi.org/10.1088/0953-8984/25/8/085507
  21. Po W, Jiarui W, Jing Z, Liejin G, Frank E. Structure defects in g-C3N4 limit visible light driven hydrogen evolution and photovoltage. J Mater Chem A 2014;2: 20338-20344. https://doi.org/10.1039/C4TA04100C
  22. Zhao B, Zhong W, Chen F, Wang P, Bie C, Yu H. High-crystalline g-C3N4 photocatalysts: Synthesis, structure modulation, and H2-evolution application. Chin J Catal. 2023;52:127–43. https://doi.org/10.1016/S1872-2067(23)64491-2
  23. Francescangeli O, Rinaldi D, Laus M, Gallot B. X-ray Diffraction Study of the Smectic C Mesophase of a Side Chain Polyacrylate Containing a Sulfide Substituted Mesogen, J Phys B Atom and Mole Phys. 1996;6(1):77-89. https://doi.org/1051/jp2:1996168
  24. Ishibashi H, Koo TY, Hor YS, Borissov A,  Radaelli PG, Horibe Y, et al. X-ray-induced disordering of the dimerization pattern and apparent low-temperature enhancement of lattice symmetry in spinel. Phys Rev B 2002;66:144-424. https://doi.org/10.1103/PhysRevB.66.144424
  25. Li Y, Wang S, Chang W, Zhang L, Wu Z, Song S, et al. Preparation and enhanced photocatalytic performance of sulfur doped terminal-methylated g-C3N4 nanosheets with extended visible-light response. J Mater Chem A 2019;7(36):20640–8. https://doi.org/10.1039/C9TA07014A
  26. Feng C, Tang L, Deng Y, Wang J, Liu Y, Ouyang X, et al. A novel sulfur-assisted annealing method of g-C3N4 nanosheet compensates for the loss of light absorption with further promoted charge transfer for photocatalytic production of H2 and H2O2. Appl Catal B Environ. 2021;281:119539. https://doi.org/10.1016/j.apcatb.2020.119539
  27. Brodusch N, Zaghib K, Gauvin R. Improving the Energy Resolution of Energy Dispersive Spectrometers (EDS) Using Richardson–Lucy Deconvolution. J Ultramic, 2020;209:112-886.
  28. Newbury DE, Ritchie Is Scanning Electron Microscopy/Energy Dispersive X‐ray Spectrometry (SEM/EDS) Quantitative? Scanning 2013;35(3):141-68. https://doi.org/10.1002/sca.21041
  29. Landi S, Segundo IR, Freitas E, Vasilevskiy M, Carneiro J, Tavares CJ. Use and misuse of the Kubelka-Munk function to obtain the band gap energy from diffuse reflectance measurements. Solid State Commun. 2022;341:114573. https://doi.org/10.1016/j.ssc.2021.114573
  30. Makuła P, Pacia M, Macyk W. How To Correctly Determine the Band Gap Energy of Modified Semiconductor Photocatalysts Based on UV–Vis Spectra. J Phys Chem Lett. 2018;9(23):6814–7. https://doi.org/ 1021/acs.jpclett.8b02892
  31. Zhang J, Hu Y, Jiang X, Chen S, Meng S, Fu X. Design of a direct Z-scheme photocatalyst: Preparation and characterization of Bi2O3/g-C3N4 with high visible light activity. J Hazard Mater. 2014;280:713–22. https://doi.org/10.1021/acs.jpclett.8b02892
  32. Bai Y, Wang PQ, Liu JY, Liu XJ. Enhanced photocatalytic performance of direct Z-scheme BiOCl–g-C3N4 photocatalysts. RSC Adv. 2014; 4(37):19456. https://doi.org/10.1039/C4RA01629G
  33. Wang X jing, Wang Q, Li F tang, Yang W yan, Zhao Y, Hao Y juan, et al. Novel BiOCl–C3N4 heterojunction photocatalysts: In situ preparation via an ionic-liquid-assisted solvent-thermal route and their visible-light photocatalytic activities. Chem Eng J. 2013;234:361–71. https://doi.org/10.1016/j.cej.2013.08.112
  34. Zhong K, Feng J, Gao H, Zhang Y, Lai K. Fabrication of BiVO4@g-C3N4(100) heterojunction with enhanced photocatalytic visible-light-driven activity. J Solid State Chem. 2019;274:142–51. https://doi.org/10.1016/j.jssc.2019.03.022
  35. Heydari A, Hajizadeh-Oghaz M, Ramezanalizadeh H. Enhanced photocatalytic and magnetic properties of SrFe12O19/g-C3N4 nanocomposites for environmental remediation. Int J Hydrog Energy 2025;151:150223. https://doi.org/10.1016/j.ijhydene.2025.150223
  36. Fernández-Catalá J, Greco R, Navlani-García M, Cao W, Berenguer-Murcia Á, Cazorla-Amorós D. g-C3N4-Based Direct Z-Scheme Photocatalysts for Environmental Applications. Catalysts 2022;12(10): 1137. https://doi.org/10.3390/catal12101137
  37. Pourshirband N, Nezamzadeh-Ejhieh A. An efficient Z-scheme CdS/g-C3N4 nano catalyst in methyl orange photodegradation: Focus on the scavenging agent and mechanism. J Mol Liq. 2021;335:116543. https://doi.org/10.1016/j.molliq.2021.116543

 

 

مواد پیشرفته در مهندسی
دوره 45، شماره 1
(شماره پیاپی 52)
فروردین 1405
صفحه 33-48

فایل ها

هم رسانی

ارجاع به این مقاله

آمار

تحت نظارت وف ایرانی