Enhanced Photocatalytic Degradation of Methyl Red Dye Via Hydrothermally Synthesized Manganese Tungstate

Yıl 2025, Cilt: 8 Sayı: 5, 1577 - 1584, 15.09.2025

Mehmet Kayhan

https://doi.org/10.34248/bsengineering.1733519

Öz

In this study, MnWO₄ nanoparticles were successfully synthesized via a CTAB-assisted hydrothermal method and evaluated for their photocatalytic degradation performance against Methyl Red (MR) dye under UV-C irradiation. Structural and morphological characterizations were performed using XRD, FTIR, SEM, and UV-DRS techniques, confirming the formation of highly crystalline monoclinic MnWO₄ with defect-rich surfaces. The photocatalytic experiments were conducted under UV-C light (254 nm) with a catalyst dosage of 0.5 g/L, initial MR concentration of 20 mg/L, and solution pH of 6.5. The synthesized MnWO₄ exhibited excellent degradation efficiency, achieving 98% MR removal within 90 minutes, outperforming several conventional photocatalysts. This work addresses a critical gap in the literature by demonstrating the enhanced activity of CTAB-modified MnWO₄ under UV-C light, offering a promising route for azo dye remediation. The findings suggest that morphology control and surface defect engineering significantly influence photocatalytic performance, making MnWO₄ a viable candidate for environmental applications.

Anahtar Kelimeler

Manganese tungstate , Hydrothermal synthesis , Methyl red , UV-C photocatalysis , Azo dye degradation , Band gap engineering

Etik Beyan

Ethics committee approval was not required for this study because of there was no study on animals or humans.

Kaynakça

• Ahmad MA, Ahmad N, Bello OS. 2015. Modified durian seed as adsorbent for the removal of methyl red dye from aqueous solutions. Appl Water Sci, 5(4): 407–423. https://doi.org/10.1007/s13201-014-0208-4
• Ahmad MA, Ahmed NB, Adegoke KA, Bello OS. 2019. Sorption studies of methyl red dye removal using lemon grass (Cymbopogon citratus). Chem Data Collect, 22: 100249. https://doi.org/10.1016/j.cdc.2019.100249
• Alharbi AA, Aldaghri O, El-Badry BA, Ibnaouf KH, Alfadhl F, Albadri A, Modwi A. 2024. Degradation of methyl red dye via fabricated Y₂O₃–MgO/g-C₃N₄ nanostructures: modification of band gap and photocatalysis under visible light. Opt Mater, 152: 115443. https://doi.org/10.1016/j.optmat.2024.115443
• Allabakshi SM, Srikar PSNSR, Gangwar RK, Maliyekkal SM. 2025. Nonthermal plasma technology for degradation of dyes in wastewater. In: Hamdaoui O (Ed.), Innovative and Hybrid Advanced Oxidation Processes for Water Treatment. Elsevier, pp: 255–278. https://doi.org/10.1016/B978-0-443-14100-3.00001-6
• Almeida MAP, Cavalcante LS, Varela JA, Li MS, Longo E. 2012. Effect of different surfactants on the shape, growth and photoluminescence behavior of MnWO₄ crystals synthesized by the microwave-hydrothermal method. Adv Powder Technol, 23(1): 124–128. https://doi.org/10.1016/j.apt.2011.10.004
• Berradi M, Hsissou R, Khudhair M, Assouag M, Cherkaoui O, El Bachiri A, El Harfi A. 2019. Textile finishing dyes and their impact on aquatic environs. Heliyon, 5(11): e02711. https://doi.org/10.1016/j.heliyon.2019.e02711
• Chakraborty AK, Ganguli S, Kebede MA. 2012. Photocatalytic degradation of 2-propanol and phenol using Au loaded MnWO₄ nanorod under visible light irradiation. J Cluster Sci, 23(2): 437–448. https://doi.org/10.1007/s10876-012-0450-6
• Gaim YT, Tesfamariam GM, Nigussie GY, Ashebir ME. 2019. Synthesis, characterization and photocatalytic activity of N-doped Cu₂O/ZnO nanocomposite on degradation of methyl red. J Compos Sci, 3(4): 93. https://doi.org/10.3390/jcs3040093
• Grass RN, Tsantilis S, Pratsinis SE. 2006. Design of high-temperature, gas-phase synthesis of hard or soft TiO₂ agglomerates. AIChE J, 52(4): 1318–1325. https://doi.org/10.1002/aic.10739
• Hassan MS, Amna T, Al-Deyab SS, Kim HC, Khil MS. 2015. Monodispersed 3D MnWO₄–TiO₂ composite nanoflowers photocatalysts for environmental remediation. Curr Appl Phys, 15(6): 753–758. https://doi.org/10.1016/j.cap.2015.03.022
• He HY, Huang JF, Cao LY, Wu JP. 2010. Photodegradation of methyl orange aqueous on MnWO₄ powder under different light resources and initial pH. Desalination, 252(1): 66–70. https://doi.org/10.1016/j.desal.2009.10.024
• Jayakumar P, Palani S, Nallathambi M, Kuppusamy K. 2024. Evaluation of MnWO₄ nanomaterial for enhanced photocatalytic degradation activity over methyl orange. Lett Appl NanoBioSci, 13(1): 1. https://doi.org/10.33263/lianbs131.001
• Kayhan E. 2025. Temperature-controlled synthesis of bismuth tungstate with enhanced photochromic properties. Int J Appl Ceram Technol, 22(3): e15079. https://doi.org/10.1111/ijac.15079
• Kayhan M, Aksoy M, Kayhan E. 2024. A facile synthesis of photocatalytic Fe(OH)₃ nanoparticles for degradation of phenol. ChemistrySelect, 9(23): e202401367. https://doi.org/10.1002/slct.202401367
• Kayhan M, Kayhan E. in press. Synthesis, characterization, and photocatalytic performance evaluation of manganese tungstate for methyl red dye degradation. Pamukkale Univ J Eng Sci, in press: 0 0. https://doi.org/10.5505/pajes.2025.27723
• Kayhan M. 2025. Comparative study of photochromic behavior of bismuth tungstate via different surfactants. Ceram Int, 51(14): 19579–19588. https://doi.org/10.1016/j.ceramint.2025.02.133
• Khaksar M, Boghaei DM, Amini M. 2015. Synthesis, structural characterization and reactivity of manganese tungstate nanoparticles in the oxidative degradation of methylene blue. C R Chim, 18(2): 199–203. https://doi.org/10.1016/j.crci.2014.04.004
• Kumar KS, Vaishnavi K, Venkataswamy P, Ravi G, Ramaswamy K, Vithal M. 2021. Photocatalytic degradation of methylene blue over N-doped MnWO₄ under visible light irradiation. J Indian Chem Soc, 98(10): 100140. https://doi.org/10.1016/j.jics.2021.100140
• Li R, Du Y, Tang C, Huang Y, Han G. 2025. Photocatalytic degradation of azo dye wastewater by thermal stripping of g-C₃N₄. In: Al-Majali Y, Wisner B, Mastorakos IN, Hunyadi Murph SE, Paramsothy M (eds) Advances in Sustainable Composites. TMS 2025. Springer, Cham. https://doi.org/10.1007/978-3-031-81057-2_17
• Luo S, Ke J, Yuan M, Zhang Q, Xie P, Deng L, Wang S. 2018. CuInS₂ quantum dots embedded in Bi₂WO₆ nanoflowers for enhanced visible light photocatalytic removal of contaminants. Appl Catal B Environ, 221: 215–222. https://doi.org/10.1016/j.apcatb.2017.09.028
• Maya-Johnson S, Gracia L, Longo E, Andres J, Leite ER. 2017. Synthesis of cuboctahedral CeO₂ nanoclusters and their assembly into cuboid nanoparticles by oriented attachment. ChemNanoMat, 3(4): 228–232. https://doi.org/10.1002/cnma.201700005
• Muthamizh S, Suresh R, Giribabu K, Manigandan R, Praveen Kumar S, Munusamy S, Narayanan V. 2015. MnWO₄ nanocapsules: synthesis, characterization and its electrochemical sensing property. J Alloys Compd, 619: 601–609. https://doi.org/10.1016/j.jallcom.2014.09.049
• Nagaraja K, Mallika B, Arunpandian M, Ravindran E, Tae Hwan O. 2025. Green synthesis of gold-decorated BaTiO₃-ZnO nanocomposites using Arabic gum polymer for efficient photocatalytic degradation of emerging textile dyes, antimicrobial, and toxicological evaluation. Int J Biol Macromol, 311: 143396. https://doi.org/10.1016/j.ijbiomac.2025.143396
• Nezzari A, Medina S, Khane Y, Boublenza H, Guezzoul M, Zoukel A, Amrani B. 2025. Photocatalytic degradation of brilliant green dye using Cu₂NiSnS₄ thin films under ultraviolet irradiation. Inorg Chem Commun, 174: 114021. https://doi.org/10.1016/j.inoche.2025.114021
• Nogami A, Suzuki T, Katsufuji T. 2008. Second harmonic generation from multiferroic MnWO₄. J Phys Soc Jpn, 77(11): 115001. https://doi.org/10.1143/JPSJ.77.115001
• Pirhashemi M, Habibi-Yangjeh A. 2018. Fabrication of novel ZnO/MnWO₄ nanocomposites with p-n heterojunction: visible-light-induced photocatalysts with substantially improved activity and durability. J Mater Sci Technol, 34(10): 1891–1901. https://doi.org/10.1016/j.jmst.2018.01.014
• Rao A, Cölfen H. 2017. Facet control in nanocrystal growth. In: Atwood JL (Ed.), Comprehensive Supramolecular Chemistry II. Elsevier, pp: 129–156. https://doi.org/10.1016/B978-0-12-409547-2.12638-1
• Rastin H, Dell’Angelo D, Sayede A, Badawi M, Habibzadeh S. 2025. Green and sustainable metal-organic frameworks (MOFs) in wastewater treatment: a review. Environ Res, 282: 122087. https://doi.org/10.1016/j.envres.2025.122087
• Sahoo S, Reddy GBT, Mahamallik P. 2024. Sunlight-assisted photocatalytic degradation of methyl red using g-C₃N₄ as metal-free photocatalyst. In: Mazumder D (ed.) Sustainable Advanced Technologies for Environmental Management. Springer Proc Earth Environ Sci. Springer, Cham. https://doi.org/10.1007/978-3-031-64006-3_1
• Shalini S, Sasikala T, Tharani D, Venkatesh R, Muthulingam S. 2024. Novel green CQDs/ZnO binary photocatalyst synthesis for efficient visible light irradiation of organic dye degradation. J Mol Liq, 410: 125525. https://doi.org/10.1016/j.molliq.2024.125525
• Shamshad J, Ur Rehman R. 2025. Innovative approaches to sustainable wastewater treatment: a comprehensive exploration of conventional and emerging technologies. Environ Sci Adv, 4(2): 189–222. https://doi.org/10.1039/D4VA00136B
• Shivaganga GS, Parameswara P, Mallikarjunaswamy C, Kumar KCS, Soundarya TL, Nagaraju G, Ranganatha VL. 2023. Green, nonchemical route for the synthesis of MnWO₄ nanostructures: photocatalytic and electrochemical performance. J Mater Sci Mater Electron, 34(25): 1791. https://doi.org/10.1007/s10854-023-11190-3
• Siahsahlan M, Mohammadi Aref S, Naghshara H, Azmayesh R. 2025. The effects of reduced graphene oxide amount on the photocatalytic performance of TiO₂ nanoparticles for hydrogen evolution. Int J Hydrogen Energy, 142: 318–329. https://doi.org/10.1016/j.ijhydene.2025.05.411
• Vosoughifar M. 2017. Preparation, characterization, and morphological control of MnWO₄ nanoparticles through novel method and its photocatalyst application. J Mater Sci Mater Electron, 28(2): 2135–2140. https://doi.org/10.1007/s10854-016-5777-6
• Wang G, Xu J, Sun Z, Zheng S. 2020. Surface functionalization of montmorillonite with chitosan and the role of surface properties on its adsorptive performance: a comparative study on mycotoxins adsorption. Langmuir, 36(10): 2601–2611. https://doi.org/10.1021/acs.langmuir.9b03673
• Wu W, Qin W, He Y, Wu Y, Wu T. 2012. The effect of pH value on the synthesis and photocatalytic performance of MnWO₄ nanostructure by hydrothermal method. J Exp Nanosci, 7(4): 390–398. https://doi.org/10.1080/17458080.2010.533293
• Xue W, He H, Zhu J, Yuan P. 2007. FTIR investigation of CTAB–Al–montmorillonite complexes. Spectrochim Acta A Mol Biomol Spectrosc, 67(3): 1030–1036. https://doi.org/10.1016/j.saa.2006.09.024
• Zargazi M, Entezari MH. 2019. Sonochemical versus hydrothermal synthesis of bismuth tungstate nanostructures: photocatalytic, sonocatalytic and sonophotocatalytic activities. Ultrason Sonochem, 51: 1–11. https://doi.org/10.1016/j.ultsonch.2018.10.010
• Zhang D, Otitoju TA, Ouyang Y, Shoparwe NF, Wang S, Li S. 2021. A review on metal ions modified TiO₂ for photocatalytic degradation of organic pollutants. Catalysts, 11(9): 1039. https://doi.org/10.3390/catal11091039
• Zheng M, Zhang H, Gong X, Xu R, Xiao Y, Dong H, Liu Y. 2013. A simple additive-free approach for the synthesis of uniform manganese monoxide nanorods with large specific surface area. Nanoscale Res Lett, 8(1): 166. https://doi.org/10.1186/1556-276X-8-166