Study on Degradation of Textile Dyes by Photocatalytic Ozonation Assisted with Tin Doped Zinc Oxide Nanorods

Document Type : Research Paper


1 Department of Chemistry, Quaid-E-Millath Govt. College for Women, Chennai, India

2 Department of Physics, Quaid-E-Millath Govt. College for Women, Chennai, India


   The current research work focuses on the synergistic effect of tin doped Zinc oxide(Sn- ZnO) nanorods in combination with ozonation for the degradation of dyes in the water released from textile industries. Well crystalline mono dispersed Sn doped ZnO (Sn-ZnO) nanorods have been synthesized by simple hydrothermal method.  The XRD results show the hexagonal wurtzite structure of the prepared catalyst. The result of EDAX and XPS revealed that Sn was doped in to ZnO lattices. FESEM image show that the sample possesses hexagonal rod morphology with an average of 1µm in length and 50 to 100nm in diameter.  Optical transmittance of the sample was recorded in the wavelength range of 300–800 nm, and the band gap was determined. The prepared nanocatalyst in combination with ozone is used for the photocatalytic ozonation (nano PCO) of the azo dyes taken for the present study. Nano PCO is carried out in a laboratory scale photocatalytic ozonation reactor.  The experiments were conducted under different ozone dosages (0.12-0.57 g/h), pH (3-9), catalyst dosage (0-2 g/L) and dye concentration (5-50 mg/L) to arrive at optimized reaction conditions for degradation of dyes by Sn-ZnO assisted PCO.  Three experimental sets (Sn-ZnO/UV, UV/O3 and Sn-ZnO/UV/O3) were carried out under optimized reaction conditions to prove the synergistic effect of ozone on Sn-ZnO.  Use of ozone with Sn-ZnO leads to 95% decolourisation of the dyes in 30 min and 79.4% mineralization in 180 min.   The reusability of the photocatalyst was checked six times and the results revealed that the efficiency of the sample slightly decreased at the end of sixth cycle.  Based on the above results, the current route is promising for the application of Sn-ZnO based nanocatalyst in combination with ozonation for wastewater treatment.


Main Subjects

  1. Saravanan, A., Deivayanai, V. C., Senthil Kumar, P., Gayathri, R., Hemavathy, R. V., Harshana, T., Gayathri, N., Krishanpandi A., “A detailed review on advanced oxidation process in treatment of wastewater: Mechanism, challenges and future outlook”, Chemosphere, 308(3) (2022) 136524.
  2. Syam Babu, D., Srivastava, V., Nidheesh, P. V., Suresh Kumar, M., “Detoxification of water and wastewater by advanced oxidation processes”, Science of the Total Environment, 695 (2019) 133961.
  3. Yang, D., Zhao, R., “Advanced Oxidation Processes (AOPs) in wastewater treatment”, Pollution Reports, 1(3) (2015) 167-176.
  4. Gogate, P. R., Pandit, A. R., “A review of imperative technologies for wastewater treatment I: oxidation technologies at ambient conditions”, Environ. Res., 8 (2004a) 501-551.
  5. Antonopoulou, M., Evgenidou, E., Lambropoulou, D., Konstantinou, I., “A review on advanced oxidation processes for the removal of taste and odor compounds from aqueous media”, Water Res., 53 (2014) 215-234.
  6. Nirmalendu, S. M., Rajesh, R., Aneek, K., Rani, A., Priya,, Nawaz, A., Saravanan, P., “A Review on Advanced Oxidation Processes for Effective Water Treatment”, Current World Environment, 12(3) (2017) 470-490.
  7. Bilinska, L., Gmurek, M., Ledakowicz, S., “Comparison between simulated textile wastewater treatment by AOPS-Biodegradability, toxicity and cost assessment”, Chemical Engineering Journal, 306 (2016) 550-559.
  8. Shrivani, M., Naji, L., “Effect of seed layer on Morphology of Zinc oxide nanorods as an electron transport layer in polymer solar cells”, International Journal of Nanoscience and Nanotechnology, 16(3) (2020) 201-208.
  9. Divya, B., Karthikeyan, C., Rajasimman, M., “Chemical synthesis of Zinc oxide nanoparticles and its application of dye decolorization”, International Journal of Nanoscience and Nanotechnology, 14 (2018) 267-275.
  10. Raha, S., Ahmaruzzaman, Md., “ZnO nanostructured materials and their potential applications: progress, challenges and perspectives”, Nanoscale Adv., 4 (2022) 1868.
  11. Baruh, S., Pak, S. K., Dutta, J., “Nanostructured zinc oxide for water treatment”, Nanoscience and Nanotechnology-Asia, 2 (2012) 90-102.
  12. Udo, M. K., Ram, E. K., Stefanakos, A. F., Hepp, D., Yogi, G., “One Dimensional-ZnO Nanostructures: Synthesis, Properties and Environmental Applications”, Sci. Semicond. Process, 16 (2013) 2070-2083.
  13. Muruganandham, M., Zhang, Y., Suri, R., Lee, G. J., Chen, P. K., Hsieh, S. H., Sillanpaa, M., Wu, J. J., “Environmental applications of ZnO materials (Review)”, Journal of Nanoscience and Nanotechnology, 15(9) (2015) 6900-6913.
  14. Aisah, N., Gustiono, D., Fauzia, V., Sugihartono, I., Nuryadi, R., “Synthesis and enhanced photocatalytic activity of Ce-doped Zinc oxide nanorods by hydrothermal method”, Materials Science and Engineering, 172 (2017) 012037.
  15. Jongnavakit, P., Amornpitoksuk, P., Suwanboon, S., Ndiege, N., “Preparation and photocatalytic activity of Cu-doped ZnO thin films prepared by the sol–gel method”, Surf. Sci., 258 (2012) 8192–8198.
  16. Zhao, J., Wang, L., Yan, X. Q., Yang, Y., Lei, Y., Zhou, J., Huang, Y. H., Gu, Y. S., Zhang, Y., “Structure and photocatalytic activity of Ni-doped ZnO nanorods”, Res. Bull., 46 (2011) 1207–1210
  17. Gopalakrishnan, R., Muthukumaran, S., “Nanostructure, optical and photoluminescence properties of Zn1−xNixO nanoclusters by co-precipitation method”, J Mater Sci: Mater Electron, 24(4) (2013) S1069–S1080.
  18. Manjula G. Nair, Nirmala, M., Rekha, K., Anukaliani, A., “Structural, optical, photocatalytic and antibacterial activity of ZnO and Co doped ZnO nanoparticles”, Lett., 65 (2011) 1797–1800.
  19. Madahi, P., Shahtahmasebi, N, Kompany, A., Mashreghi, M., Bagheri-Mohagheghi, M. M., Hosseini, A., “Deposition and characterization of ZnO:Mg thin films: the study of antibacterial properties”, Scr., 84 (2011) 035801-5.
  20. Suwanboon, S., Amornpitoksuk, P., Bangrak, P., Muensit, N., “Structural, optical and antibacterial properties of nanocrystalline Zn 1–xLaxO compound semiconductor”, Sci. Semicond. Process, 16 (2013) 504–512.
  21. Rekha, K., Nirmala, M., Nair, Manjula G., Anukaliani, A., “Structural, optical, photocatalytic and antibacterial activity of zinc oxide and manganese doped zinc oxide nanoparticles”, Physica B, 405 (2010) 3180–3185.
  22. Sonal, S., Kaur, J., Namgyak, T., Sharma, R., “Cu doped ZnO nanoparticles: synthesis, structural and electrical properties”, Physica B: Condensed Matter, 407 (2012) 1223–1226
  23. Milenova, K., Stambolova, I., Blaskkov, V., Eliyas, A., Vassilev, S., Shipochka,M., “The effect of introducing copper dopant on the photocatalytic activity of ZnO nanoparticles”, Journal of the University of Chemical Technology, 48 (2013) 259–64.
  24. Nakata, Y., Okada, T., Maeda, M., “Deposition of ZnO film by pulsed laser deposition at room temperature,” Surface Sci, 197 (2002) 368–70
  25. Chen, B. J., Sun, X. W., Xu, C. X., Tay, B. K., “Growth and characterization of zinc oxide nano/micro fibres by thermal chemical reactions and vapour transport deposition in air”, E, 21 (2004) 103–107
  26. Anaraki Firooz, A., Keyhani, M., “The effect of different dopants (Cr, Mn, Fe, Co, Cu and Ni) on photocatalytic properties of ZnO nanostructures”, International Journal of Nanoscience and Nanotechnology, 16(1) (2020) 59-65.
  27. Lee, H. J., Kim, J. H., Park, S. S., Hong, S. S. Lee, G. D., “Degradation kinetics for photocatalytic reaction of methyl orange over Al-doped ZnO nanoparticles”, Journal of Industrial and Engineering Chemistry, 25 (2015) 199-206.
  28. Yarahmadi, M., Maleki-Ghaleh, H., Emami Mehr, M., Dargahi, Z., Rasouli, F., Siadati, M. H., “Synthesis and characterization of Sr-doped ZnO nanoparticles for photocatalytic applications”, Journal of Alloys and Compounds, 853 (2021) 157000.
  29. Pandian, L., Rajasekaran, R., Govindan, P., “Synergistic effect of ozone on cadmium doped zinc oxide nanocatalyst for the degradation of textile dyeing wastewater”, Res. Express, 6 (2019) 085513.
  30. Siva, N., Sakthi, D., Ragupathy, S., Arun, V., Kannadasan, N., “Synthesis, structural, optical and photocatalytic behavior of Sn doped ZnO nanoparticles”, Materials Science and Engineering: B, 253 (2020) 114497.
  31. Sun, J. H., Dong, S. Y., Feng, J. L., Yin, X. J., Zhao, X. C., “Enhanced sunlight photocatalytic performance of Sn-doped ZnO for methylene bluedegradation”, Mol. Catal. A: Chem., 335 (2011) 145-150.
  32. Gottschalk, C., Libra, J. A., Saupe, A., “Ozonation of water and waste water: a practical guide to understanding ozone and its applications”, John Wiley & Sons, (2009).
  33. Audenaert, W. T., Vandierendonck, D., Van Hulle, S. W., Nopens, I., “Comparison of ozone and HO induced conversion of effluent organic matter (EfOM) using ozonation and UV/H2O2 treatment” Water Res., 47(7) 2013, 2387–2398.
  34. Li, L., Zhu, W., Chen, L., Zhang, P., Chen, Z., “Photocatalytic ozonation of dibutylphthalate over TiO2 film”, of Photochem. Photobiol. A: Chemistry., 175 (2005) 172-177.
  35. Addamo, M., Augugliaro, V., Lopez, E. G., Loddo, Marci, G., Palmisano, L., “Oxidation of oxalate ion in aqueous suspensions of TiO2 by photocatalysis and ozonation”, Today., 107-108 (2005) 612-618.
  36. Ilisz, I., Bokro., A., Dombi, A., “TiO2-Based Heterogeneous Photocatalytic Water Treatment combined with Ozonation”, Ozone: Sci. Engg., 26 (2004) 585-594.
  37. Biglari, H., Adsharnia, M., Alipour, V., Khosravi, R., Sharafi, K., Mahvi, A. H., “A review and investigation of the effect of nanophotocatalytic ozonation process for phenolic compound removal from real effluent of pulp and paper industry”, Sci. Pollut. Res. Int, 24(4) (2017) 4105-4116.
  38. Rajeswari, R., Kanmani, S., “Degradation of Pesticide by Photocatalytic Ozonation process and study of Synergistic effect by Comparison with photocatalysis and UV/ozonation processes”, Journal of Advanced Oxidation Technologies, 12(2) (2009) 208-214.
  39. Agustina, T. E., Ang, H. M., Vareek, V. K., “A review of synergistic effect of photocatalysis and ozonation on wastewater treatment”, Of Photochem. Photobiol. C: Photochemistry Reviews, 6 (2005) 264-273.
  40. American Public Health Association, “Standard methods for the examination of water and wastewater”, 21-st edition, Washington DC, USA, (2005).
  41. Chewki, Z., Khalilr, A., Denis, C., Mohamed, A., Saad, H., “Influence of Sn Low Doping on the Morphological, Structural and Optical Properties of ZnO Films Deposited by Sol Gel Dip-Coating”, Advances in Materials Physics and Chemistry, 4 (2014) 93-104.
  42. Sadia, A., Shaheer Akhtar, M., Hyunt-Kee, S., Young, S. K., Hyung, S. S., “Influence of Sn doping on ZnO nanostructures from nanoparticles to spindle shape and their photoelectrochemical properties for dye sensitized solar cells”, Chemical Engineering Journal, 187 (2012)351-356.
  43. Tauc, J., Grigorovici, R., Vancu, A., Stat. Sol., 15 (1966) 627-637.
  44. Zegadi, C., Abdelkebir, K., Chaumont, ,D., Adnane, M., Hamzaoui, S., “Influence of Sn low doping on the morphological, structural and optical properties of ZnO films deposited by sol gel dip-coating”, Mater. Phys. Chem., 4 (2014) 93–104.
  45. Cernigoj, U., Stangar, U. L., Trebse, P., “Degradation of neonicotinoid insecticides by different advanced oxidation processes and studying the effect of ozone on TiO2 photocatalysis”, Catal. B: Environmental, 75 (2007) 231-240.
  46. Pandian, L., Rajasekaran, R., Govindan, P., “Synthesis, characterization and application of Cu doped ZnO nanocatalyst for photocatalytic ozonation of textile dye and study of its reusability”, Res. Express, 5 (2018)115505.
  47. Subash, B., Krishnakumar, B., Swaminathan, M., Shanthi, M., “Highly Efficient, Solar Active, and Reusable Photocatalyst: Zr-Loaded Ag−ZnO for Reactive Red 120 Dye Degradation with Synergistic Effect and Dye-Sensitized Mechanism”, Langmuir, 29 (2013) 939−949
  48. Diego, H. Q., Ana, R., Pedro, M. A., Beltran, F. J., Plucinski, P. K., “Enhanced activity and reusability of TiO2 loaded magnetic activated carbon for solar photocatalytic ozonation”, Applied Catalysis B: Environmental, 144 (2014) 96-106.
  49. Akhmal Saadon, S., Sathishkumar, P., Mohd Yusoff, A. R., Hakim Wirzal, M. D., Rahmalan M. T., Nur, H., “Photocatalytic activity and reusability of ZnO layer synthesised by electrolysis, hydrogen peroxide and heat treatment”, Environ Technol, 37(15) (2016) 1875-1882.
  50. Mehralipour, J., Darvishali, S., Bagheri, S., Kermani, M., “Photocatalytic ozonation process in oxytetracyline degradation in aqueous solution: composite characterization optimization, energy consumption and by-products”, Scientific Reports, 13 (2023) 11113.