Preparation of a filter bed coupled with Mn-TiO2/ZnO nanocomposite for the treatment of micro-pollutants in municipal wastewater

Document Type : Original Article


1 Department of Water and Health, JSS Academy of Higher Education and Research, Mysuru, India-570015

2 Center for Water, Food and Energy, The GREENS trust, Harikaranahalli, Dombaranahalli Post, Turuvekere Taluka, Tumkur District, Karnataka, India-572215


Technical advancement is urgently required for the degradation of micro-pollutants in municipal wastewater. The present study aimed to describe the preparation of a filter-bed Mn-TiO2/ZnO nanocomposite and degradation of micro-pollutants in real-time municipal wastewater obtained from Kesare wastewater treatment plant in Mysore district, India. Activated carbon and sand were used for the preparation of the filter bed, and activated carbon was prepared using agricultural wastes (coconut shells). Meanwhile, the visible light-responsive Mn-TiO2/ZnO composite was prepared using the mild sol-gel technique. The composites were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, and photocatalytic techniques. High crystallinity, considerable shift in the band gap energy, and adequate photocatalytic activity under the visible light range were observed. In addition, the filter bed coupled with the Mn-TiO2/ZnO nanocomposite functioned efficiently in the degradation of the common pollutants under LED irradiation as the driving source of energy.


  1. Shivaraju HP, Muzakkira N, Shahmoradi B. Photocatalytic treatment of oil and grease spills in wastewater using coated N-doped TiO2 polyscales under sunlight as an alternative driving energy. Int J Environ Sci Technol 2016; 13: 2293–302.
  2. Shivaraju HP, Midhun G, Anil Kumar KM, Pallavi S, Pallavi N, Shahmoradi B. Degradation of selected industrial dyes using Mg-doped TiO2 polyscales under natural sun light as an alternative driving energy. Appl Water Sci 2017; 7: 3937–48.
  3. Naldoni A, Allieta M, Santangelo S. Effect of nature and location of defects on bandgap narrowing in black TiO2 nanoparticles. J Am Chem Soc 2012; 134(18): 7600–03.
  4. Choi SK, Kim S, Lim SK, Park H. Photocatalytic comparison of TiO2 nanoparticles and electrospun TiO2 nanofibers: Effects of mesoporosity and interparticle charge transfer. J Phy Chem C 2010; 114(39): 16475–80.
  5. Cho MH, Lee GH. Growth of high quality rutile TiO2 thin film using ZnO buffer layer on Si(100) substrate. Thin Solid Films 2008; 516(17): 5877-80.
  6. Hariharan C. Photocatalytic degradation of organic contaminants in water by ZnO nanoparticles: Revisited. Appl Catal A-Gen 2006; 304: 55-61.
  7. Zhou Y, Wu WB, Hu G, Wu HT, Cui SG. Hydrothermal synthesis of ZnO nanorod arrays with the addition of polyethyleneimine. Mat Res Bull 2008; 43(8-9): 2113-8.
  8. Zhou M, Yu J. Preparation and enhanced day light induced photocatalytic activity of C,N,S-tridoped titanium dioxide powders. J Hazard Mater 2008; 152(3): 1229–36.
  9. Tan ST, Chen BJ, Sun X, Fan W, Kwok HS, Zhang XH, et al. Blueshift of optical band gap in ZnO thin films grown by metal-organic chemical-vapor deposition. J Appl phy 2005; 98(1): 013505-5.
  10. Kumar SG, Devi LG. Review on modified TiO2 photocatalysis under UV/visible light: Selected results and related mechanisms on interfacial charge carrier transfer dynamics. J Phys Chem A 2011; 115(46): 13211–41.
  11. Shivaraju HP. Hydrothermal preparation of novel photocatalytic composite, TiO2 deposited calcium alumino-silicate beads and their photocatalytic applications. Integr Publ Assoc 2011; 1(7): 1476–91.
  12. Shivaraju HP, Chandrashekar CK. Photocatalytic removal of organic pollutants in silk industrial effluents by ZnO deposited CASB supported composite. Int J Res Chem Environ 2012; 2(2): 26-31.
  13. Saleh R, Febiana Djaja N. Transition-metal-doped ZnO nanoparticles: Synthesis, characterization and photocatalytic activity under UV light. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2014; 130: 581-90.
  14. Umaralikhan L, Jamal Mohamed Jaffar M. Green synthesis of ZnO and Mg doped ZnO nanoparticles, and its optical properties. J Mate Sci: Mater Electronics 2017; 28(11): 7677-85.
  15. Chang Sung Lim. Synthesis and characterization of TiO2-ZnO nanocomposite by a two-step chemical method. J Ceram Process Res 2010; 11(5): 631-5.
  16. Liao DL, Badour CA, Liao BQ. Preparation of nanosized TiO2/ZnO composite catalyst and its photocatalytic activity for degradation of methyl orange. J Photochem Photobiol A 2008; 194(1): 11–19.
  17. Chen S, Chen L, Gao S, Cao G. The preparation of coupled SnO2/TiO2 photocatalyst by ball milling. Mater Chem Phys 2006; 98: 116–20.
  18. Zhang XW, Lei LC. Preparation of photocatalytic Fe2O3–TiO2 coatings in one step by metal organic chemical vapor deposition. Appl Surf Sci 2008; 254(8): 2406–12.
  19. Neppolian B, Wang Q, Yamashita H, Choi H. Synthesis and characterization of ZrO2–TiO2 binary oxide semiconductor nanoparticles: Application and interparticle electron transfer process. Appl Catal A: Gen 2007; 333(2): 264–71.
  20. Li J, Liu L, Yu Y, Tang Y, Li H, Feipeng D. Preparation of highly photocatalytic active nano-size TiO2–Cu2O particle composites with a novel electrochemical method. Electrochem Comm 2004; 6(9): 940–3.
  21. Liu Y, Xie CS, Li J, Zou T, Zeng DW. New insights into the relationship between photocatalytic activity and photocurrent of TiO2/WO3 nanocomposite. Appl Catal A 2012; 433-434: 81-7.
  22. Ren CJ, Qiu W, Chen YQ. Physicochemical properties and photocatalytic activity of the TiO2/SiO2 prepared by precipitation method. Sep Purif Technol 2013; 107: 264-72.
  23. Ma BJ, Kim JS, Choi CH, Woo SI. Enhanced hydrogen generation from methanol aqueous solutions over Pt/MoO3/TiO2 under ultraviolet light. Int J Hydrog Energy 2013; 38: 3582–87.
  24. Gui Y, Li S, Xu J, Li C. Study of TiO2-doped ZnO thick film gas sensors enhanced by UV light at room temperature. Microeletron J 2008; 39: 1120-5.
  25. Kansal SK, Singh M, Sud D. Studies on TiO2/ZnO photocatalysed degradation of lignin. J Hazard Mater 2008; 153: 412-7.
  26. Zha R, Nadimicherla R, Guo X. Ultraviolet photocatalytic degradation of methyl orange by nanostructured TiO2/ZnO heterojunctions. J Mater Chem A 2015; 3: 6565–74.
  27. Hu Z, Chen G. Novel nanocomposite hydrogels consisting of layered double hydroxide with ultrahigh tensibility and hierarchical porous structure at low inorganic content. Adv Mater 2014; 26: 5950–6.
  28. Abdel Aal, Barakat MA, Mohamed RM. Electrophoreted Zn-TiO2-ZnO nanocomposite coating films for photocatalytic degradation of 2-chlorophenol. Appl Surf Sci 2008; 254(15): 4577–83.
  29. Wang LS, Xiao MW, Huang XJ, Wu YD. Synthesis, characterization, and photocatalytic activities of titanate nanotubes surface-decorated by zinc oxide nanoparticles. J Hazard Mater 2009; 161(1): 49–54.
  30. Rice EW, Baird RB, Eaton AD, Clesceri LS. APHA, Standard methods for examination of water and wastewater, 22nd edn. American Public Health Association, Washington, D; 2012.
  31. Norlida K, Kasim MF, Roshidah R. Band Gap narrowing and widening of ZnO nanostructures and doped materials. Nanoscale Res Lett 2015; 10: 346.
  32. Zhang M, An T, Liu X, Hu X, Sheng G, Fu J. Preparation of a high-activity ZnO/TiO2 photocatalyst via homogeneous hydrolysis method with low temperature crystallization. Mater Lett 2010; 64(17): 1883–6.
  33. Gao J, Guan F, Ma Y, Yang W, Kang J, Deng H, et al. Preparation of CeO2 nanoparticles and its application to ion-selective electrodes based on acetyl cellulose. Rare metals 2001; 20: 217.
  34. Babitha KK, Sreedevi A, Priyanka KP, Boby S, Thomas V. Structural characterization and optical studies of CeO2 nanoparticles synthesized by chemical precipitation. Indian J pure Appl Phy 2015; 53: 596-603.
  35. Abinaya C, Marikkannan M, Manikandan M, Mayandi J, Suresh P, Shanmugaiah V, et al. Structural and optical characterization and efficacy of hydrothermal synthesized Cu and Ag doped zinc oxide nanoplate bactericides. Mater Chem Phy 2016; 184: 172-82.
  36. Hosseini SM, Sarsari IA, Kameli P, Salamati H. Effect of Ag doping on structural, optical, and photocatalytic properties of ZnO nanoparticles. J Alloys Compd 2015; 640: 408-15.
  37. Katarzyna SS, Adam K, Adam P, Joanna G, Grzegorz N, Stefan J, et al. TiO2-ZnO binary oxide systems: Comprehensive characterization and tests of photocatalytic activity. Materials 2018; 11(5): 1-19.
  38. Praveen P, Viruthagiri G, Mugundan S, Shanmugam N. Sol-gel synthesis and characterization of pure and Manganese doped TiO2 nanoparticles- a new NLO active material. Spectrochim Acta A Mol. Biomol. Spectrosc 2014; 120: 548-57.
  39. Wang L, Fu X, Han Y, Chang E, Wu H, Wang H, et al. Preparation, characterization, and photocatalytic activity of TiO2/ZnO nanocomposites. J Nanomater 2013; 2013: 1-6
  40. Abdel-Gawad SA, Mohamed SM, Abdel Aziz HM. Adsorption study for chemical oxygen demand removal from aqueous solutions using alginate beads with entrapped activated carbon. J Indian Water Resour Soc 2017; 37(4): 8-16.
  41. Hassan AH, Abdel ASM. Removal of nitrate and nitrite anions from wastewater using activated carbon derived from rice straw. J Environ Anal Toxicol 2016; 6(1): 346.
  42. Lida T, Amano Y, Machida M, Imazeki F. Effect of surface property of activated carbon on adsorption of nitrate ion. Chem Pharm Bull (Tokyo) 2013; 61(11): 1173-7.
  43. Giles CH, MacEwan TH, Nakhawa SN, Smith A. Studies in adsorption. Part XI. A system of classification of solution adsorption isotherms, and its use in diagnosis of adsorption mechanisms and in measurement of specific surface areas of solids. J Chem Soc 1960: 3973-93.