Titanium dioxide Sol–Gel/Zinc oxide Sol–Gel and Titanium dioxide Sol–Gel/powdered Zinc Oxide-coated clay beads in photocatalytic reactor

Document Type : Research Paper

Authors

1 Faculty of Ocean Engineering Technology, University Malaysia Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia

2 Unidad Académica Preparatoria, Plantel II, Universidad Autónoma de Zacatecas, Zacatecas, Zac 98068, México

Abstract

Nowadays, immobilized photocatalyst clay beads have attracted considerable research interest due to their outstanding properties, including enhanced stability, easy recovery and reuse, and reduced secondary pollution. In this study, novel titanium dioxide/zinc oxide composites were synthesized via the sol–gel method and immobilized on clay beads using the dip-coating process. Various titanium dioxide/zinc oxide ratios were used to obtain different composites. For the immobilization procedure, four titanium dioxide/zinc oxide layers were coated on clay beads, dried in the oven at 100°C for 30 min, and subsequently calcined at 2°C/min up to 500°C. The coated beads were characterized using Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). Photocatalytic degradation experiments were conducted to test their performance using methylene blue as a model pollutant. The highest methylene blue degradation efficiency was achieved with pure titanium dioxide-coated clay beads. All titanium dioxide/zinc oxide composites maintained their photocatalytic performance after five consecutive recyclability experiments. This work aims to demonstrate a reproducible, scalable, and economic immobilization procedure for single and composite photocatalysts on clay beads with outstanding photocatalytic performances for wastewater treatment.

Graphical Abstract

Titanium dioxide Sol–Gel/Zinc oxide Sol–Gel and Titanium dioxide Sol–Gel/powdered Zinc Oxide-coated clay beads in photocatalytic reactor

Keywords

Main Subjects


[1] El Nemr, A., Helmy, E. T., Gomaa, E. A., Eldafrawy, S., & Mousa, M. (2019). Photocatalytic and biological activities of undoped and doped TiO₂ prepared by green method for water treatment. Journal of Environmental Chemical Engineering, 7, 103385.
[2]Moorthy, A. K., Rathi, B. G., Shukla, S. P., Kumar, K., & Bharti, V. S. (2021). Acute toxicity of textile dye methylene blue on growth and metabolism of selected freshwater microalgae. Environmental Toxicology and Pharmacology, 82, 103552.
[3] Haider, A. J., Jameel, Z. N., & Al-Hussaini, I. H. (2019). Review on: Titanium dioxide applications. Energy Procedia, 157, 17–29.
[4] Rayati, S., Bathaee, H., & Badiei, A. (2024). Catalytic activity of Fe/Mn porphyrins grafted on graphitic carbon nitride in the heterogeneous oxidation of olefins. Applied Organometallic Chemistry, 38(11).
[5] Slama, H. B., Bouket, A. C., Pourhassan, Z., Alenezi, F. N., Silini, A., Cherif-Silini, H., & Belbahri, L. (2021). Diversity of synthetic dyes from textile industries, discharge impacts and treatment methods. Applied Sciences, 11, 6255.
[6] Khan, I., Saeed, K., Zekker, I., Zhang, B., Hendi, A. H., Ahmad, A., & Ahmad, S., et al. (2022). Review on methylene blue: Its properties, uses, toxicity and photodegradation. Water, 14(2), 242.
[7] Zamel, D., & Khan, A. U. (2021). Bacterial immobilization on cellulose acetate-based nanofibers for methylene blue removal from wastewater: Mini-review. Inorganic Chemistry Communications, 131, 108766. https://doi.org/10.1016/j.inoche.2021.108766
[8] Mirhosseyni, M. S., Mohammadi Ziarani, G., & Badiei, A. (2025). Catalytic development of boron and sulphur-doped g-C₃N₄ supported Cu-MOF composite for nitroarenes reduction reaction. Journal of Molecular Structure, 1321, 139763.
[9] Malekshahi Byranvand, M., Nemati Kharat, A., Fatholahi, L., & Malekshahi Beiranvand, Z. (2013). A review on synthesis of nano-TiO₂ via different methods. Journal of Nanostructures, 3(1), 1–9.
[10] Pirhashemi, M., Habibi-Yangjeh, A., & Pouran, S. R. (2018). Review on the criteria anticipated for the fabrication of highly efficient ZnO-based visible-light-driven photocatalysts. Journal of Industrial and Engineering Chemistry, 62, 1–25.
[11] Qiu, R., Zhang, D., Mo, Y., Song, L., Brewer, E., Huang, X., & Xiong, Y. (2008). Photocatalytic activity of polymer-modified ZnO under visible light irradiation. Journal of Hazardous Materials, 156, 80–85.
[12] Taylor, C. M., Ramirez-Canona, A., Wenk, J., & Mattia, D. (2019). Enhancing the photo-corrosion resistance of ZnO nanowire photocatalysts. Journal of Hazardous Materials, 378, 120799.
[13] Daghrir, R., Drogui, P., & Robert, D. (2013). Modified TiO₂ for environmental photocatalytic applications: A review. Industrial & Engineering Chemistry Research, 52(10), 3581–3599.
[14] Pan, L., Shen, G.-Q., Zhang, J. W., Wei, X. C., Li, Wang, J. J., Xou, X., & Zhang, X. (2015). TiO₂–ZnO composite sphere decorated with ZnO clusters for effective charge isolation in photocatalysis. Industrial & Engineering Chemistry Research, 54(18), 7226–7232.
[15] Habib, M. A., Shahadat, M. T., Bahadur, N. M., Ismail, I. M. I., & Mahmood, A. J. (2013). Synthesis and characterization of ZnO-TiO₂ nanocomposites and their application as photocatalysts. International Nano Letters, 3, 5.
[16] Dinari, A., & Mahmoudi, J. (2022). Response surface methodology analysis of the photodegradation of methyl orange dye using synthesized TiO₂/Bentonite/ZnO composites. Advances in Environmental Technology, 1, 31–46.
[17] Azha, S. F., Shahadat, M., Ismail, S., Ali, S. W., & Ahammad, S. Z. (2021). Prospect of clay-based flexible adsorbent coatings as cleaner production technique in wastewater treatment, challenges, and issues: A review. Journal of the Taiwan Institute of Chemical Engineers, 120, 178–206.
[18] Srikanth, B., Goutham, R., Narrayan, R. B., Ramprasath, A., Gopinath, K. P., & Sankaranarayanan, A. R. (2017). Recent advancements in supporting materials for immobilised photocatalytic applications in wastewater treatment. Journal of Environmental Management, 200, 60–78.
[19] Hakki, H. K., Allahyari, S., Rahemi, N., & Tasbihi, M. (2019). Surface properties, adherence, and photocatalytic activity of sol–gel dip-coated TiO₂–ZnO films on glass plates. Comptes Rendus Chimie, 22(6), 393–40.
[20] Anusuya, N., Pragathiswaran, C., & Mary, J. V. (2021). A potential catalyst-TiO₂/ZnO based chitosan gel beads for the reduction of nitro-aromatic compounds aggregated sodium borohydride and their antimicrobial activity. Journal of Molecular Structure, 1236, 130197.
[21] Iazdani, F., & Nezamzadeh-Ejhieh, A. (2021). The photocatalytic rate of ZnO supported onto natural zeolite nanoparticles in the photodegradation of an aromatic amine. Environmental Science and Pollution Research, 28, 53314–53327.
[22] Hung, M. C., Yuan, S. Y., Hung, C. C., Cheng, C. L., Ho, H. C., & Ko, T. H. (2014). Effectiveness of ZnO/carbon-based material as a catalyst for photodegradation of acrolein. Carbon, 66, 93–104.
[23] Isik, Z., Bilici, Z., Adiguzel, S. K., Yatmaz, H. C., & Dizge, N. (2019). Entrapment of TiO₂ and ZnO powders in alginate beads: Photocatalytic and reuse efficiencies for dye solutions and toxicity effect for DNA damage. Environmental Technology & Innovation, 14, 100358.
[24] Tian, S., Feng, Y., Zheng, Z., & He, Z. (2023). TiO₂-based photocatalytic coatings on glass substrates for environmental applications. Coatings, 13(8), 1472.
[25] Al-Wasidi, A. S., Ahmed, M. A., Ahmed, H. A., Mahmoud, S. A., & Mohamed, A. A. (2025). Enhanced indigo carmine dye removal via chitosan-modified NiO-g-C₃N₄ catalyst: Adsorption and photocatalysis studies. International Journal of Biological Macromolecules, 320, 145669.
[26] Osman, H., Yılmaz, S. I., Uğurlu, M., Vaizogullar, A. I., & Chaudhary, A. J. (2025). Synthesis and characterisation of activated carbon supported catalysts: Photocatalytic degradation of olive wastewater solutions using these catalysts. Journal of Sol-Gel Science and Technology. Advance online publication.
[27] Han, H., Rafiq, M. K., Zhou, T., Xu, R., Masek, O., & Li, X. (2019). A critical review of clay-based composites with enhanced adsorption performance for metal and organic pollutants. Journal of Hazardous Materials, 369, 780–796.
[28] Kamarudin, N. S., Jusoh, R., Setiabudi, H. D., Sukor, N. F., & Shariffuddin, J. H. (2021). Potential nanomaterials application in wastewater treatment: Physical, chemical and biological approaches. Materials Today: Proceedings, 42, 107–114.
[29] Manova, E., Aranda, P., Martín-Luengo, M. A., Letaïef, S., & Ruiz-Hitzky, E. (2010). New titania-clay nanostructured porous materials. Microporous and Mesoporous Materials, 131(1–3), 252–260.
[30] Mishra, A., Mehta, A., & Basu, S. (2018). Clay supported TiO₂ nanoparticles for photocatalytic degradation of environmental pollutants: A review. Journal of Environmental Chemical Engineering, 6(5), 6088–6107.
[31] Mueller, B. (2015). Experimental interactions between clay minerals and bacteria: A review. Pedosphere, 25(6), 799–810.
[32] Verma, A., Samanta, S. B., Bakhshi, A. K., & Agnihotry, S. A. (2005). Effect of stabilizer on structural, optical and electrochemical properties of sol–gel derived spin coated TiO₂ films. Solar Energy Materials and Solar Cells, 88(1), 47–64.
[33] Munguti, L., & Dejene, F. (2021). Effects of Zn:Ti molar ratios on the morphological, optical and photocatalytic properties of ZnO–TiO₂ nanocomposites for application in dye removal. Materials Science in Semiconductor Processing, 128, 105786.
[34] Rajabi, S., Hashemi, H., Samaei, M. R., Nasiri, A., Azhdarpoor, A., Yousefinejad, S., & Sartaj, M. (2024). Enhanced sonophoto-catalytic and adsorption capabilities of Fe₃O₄@MC/MWCNT-CuO/Ag for petrochemical organic pollutants degradation from industrial process streams. Arabian Journal of Chemistry, 17(11), 105994.
[35] Zinatloo-Ajabshir, S., Rakhshani, S., Mehrabadi, Z., Farsadrooh, M., Feizi-Dehnayebi, M., Rakhshani, S., Dušek, M., Eigner, V., Rtimi, S., & Aminabhavi, T. M. (2024). Novel rod-like [Cu(phen)₂(OAc)]·PF₆ complex for high-performance visible-light-driven photocatalytic degradation of hazardous organic dyes: DFT approach, Hirshfeld and fingerprint plot analysis. Journal of Environmental Management, 350, 119545.
[36] Rajabi, S., Hashemi, H., Samaei, M. R., Nasiri, A., Azhdarpoor, A., Yousefinejad, S., Sartaj, M., & Isazadeh, S. (2025). Magnetic Ag⁰ and CuO-doped bio-sonocatalyst multi-walled carbon nanotube for synergized degradation of monoethylene glycol from gas refinery effluents. Journal of Water Process Engineering, 77, 108330.
[37] Bansal, P., & Verma, A. (2017). Synergistic effect of dual process (photocatalysis and photo-Fenton) for the degradation of cephalexin using TiO₂ immobilized novel clay beads with waste fly ash/foundry sand. Journal of Photochemistry and Photobiology A: Chemistry, 342, 131–142.
[38] Cob-Cantú, J. R., Lopez-Velazquez, K., Ronderos-Lara, J. G., Hoil-Canul, E. R., Castillo-Quevedo, C., Maldonado-Lopez, L. A., & Cabellos-Quiroz, J. L. (2025). TiO₂ nanoparticles immobilized on mortar spheres as a strategy for efficient photocatalyst reuse: New UV reactor design for dye removal. Frontiers in Chemistry, 13, 1581274.