Highly Stable Photocatalytic Removal of Paraquat Dichloride using ZnO/TiO2 supported on PVC





composite ZnO/TiO2, supported nanostructures, paraquat dichloride, photocatalytic degradation


This study presents on ZnO/TiO2 supported on PVC (ZnO/TiO2@PVC) in the photocatalytic removal of paraquat dichloride. The ZnO/TiO2@PVC was characterized using XRD, FESEM-EDX, FTIR, and AFM. Findings indicated that ZnO/TiO2@PVC allowed degradation of paraquat dichloride under UV irradiation by the rate of up to 73%. XRD pattern indicated the presence of both TiO2(anatase) and ZnO (zincite) crystalline as well as PVC amorphous structures. FESEM and AFM results revealed the observed shape and surface of TiO2 interconnected nanowires with ZnO nanorods uniformly distributed according to EDX mapping. The reduced surface roughness was also shown in the supported photocatalyst. FTIR analysis clearly demonstrate the combined spectra of immobilised ZnO/TiO2 powder catalyst onto the PVC in the composite. Kinetic study of the degradation process was performed according to pseudo-first-order and the influence of ZnO/TiO2 coating onto PVC polymer and initial paraquat concentration were investigated on the treatment performance. Under optimized condition (pH = 7, PQ =20 mg/L and catalyst coating =15%), the stability and reusability of the supported catalyst was also evaluated over ten sequential treatment runs, and the catalyst maintain high reactivity. High recyclability of the ZnO/TiO2@PVC composites as catalyst in photodegradation processes are also reported in this study.

Author Biography

Susilawati Toemen, Universiti Teknologi Malaysia

Jabatan Kimia, Fakulti Sains, UTM


R. M. Cámara, E. Crespo, R. Portela et al., “Enhanced photocatalytic activity of TiO2 thin films on plasma-pretreated organic polymers,” Catalysis Today, vol. 1, no. 230, pp 145–151, 2014.

B. Srikanth, R. Goutham, R. B. Narayan et al., “Recent advancements in supporting materials for immobilised photocatalytic applications in wastewater treatment,” Journal of environmental management, vol. 1, no. 200, pp. 60–78, 2017.

R. Linacero, M. L. Rojas-Cervantes, and J. D. Lopez-Gonzalez, “Preparation of xTiO2·(1−x) Al2O3 catalytic supports by the sol-gel method: physical and structural characterization,” Journal of materials science, vol. 35, no. 13, pp. 3279–3287, 2000.

M. Nawi and S. M. Zain, “Enhancing the surface properties of the immobilized Degussa P-25 TiO2 for the efficient photocatalytic removal of methylene blue from aqueous solution,” Applied Surface Science, vol. 258, no. 16, pp. 6148–6157, 2012.

K. Guesh, Á. Mayoral, Y. Chebude et al., “Effect of thermal treatment on the photocatalytic behavior of TiO2 supported on zeolites,” New Journal of Chemistry, vol. 42, no. 14, pp. 12001–12007, 2018.

Y. Yang, S. H. Zhan, X. C. Gao et al., “Degradation of toluene using modified TiO2 as photocatalysts,” In Advanced Materials Research, vol. 669, pp. 7–18, 2013.

S. Vankova, C. Francia, J. Amici et al., “Influence of Binders and Solvents on Stability of Ru/RuOx Nanoparticles on ITO Nanocrystals as LiO2 Battery Cathodes,” Chemsuschem, vol. 10, no. 3, pp. 575–586, 2017.

O. Ounas, A. A. El-Foulani, B. Lekhlif, and J. Jamal-Eddine, “Immobilization of TiO2 into a poly methyl methacrylate (PMMA) as hybrid film for photocatalytic degradation of methylene blue,” Materials Today Proceedings, vol. 22, pp. 35–40, 2020.

D. K. Hwang, Y.-G. Shul, and K. Oh, “Photocatalytic Application of Au–TiO2 Immobilized in Polycarbonate Film,” Industrial & Engineering Chemistry Research, vol. 52, no. 50, pp. 17907–17912, 2013.

R. Ata, O. Sacco, V. Vaiano et al., “Visible light active N-doped TiO2 immobilized on polystyrene as efficient system for wastewater treatment,” Journal of Photochemistry and Photobiology A: Chemistry, vol. 348, pp. 255–262, 2017.

J. Shen, R. Steinbach, J. M. Tobin et al., “Photoactive and metal-free polyamide-based polymers for water and wastewater treatment under visible light irradiation,” Applied Catalysis B: Environmental, vol. 193, pp. 226–233, 2016.

J. Velásquez, S. Valencia, L. Rios, G. Restrepo, and J. Marín, “Characterization and photocatalytic evaluation of polypropylene and polyethylene pellets coated with P25 TiO2 using the controlled-temperature embedding method,” Chemical engineering journal, vol. 203, pp. 398–405, 2012.

R. V. Aquino, A. A. Barbosa, L. B. Ribeiro et al., “Degradation of leaf green food dye by heterogeneous photocatalysis with TiO2 over a polyethylene terephthalate plate,” Chemical Papers, vol. 73, no. 10, pp. 2501–2512, 2019.

A. Pourzad, H. R. Sobhi, M. Behbahani et al., “Efficient visible light-induced photocatalytic removal of paraquat using N-doped TiO2@SiO2@Fe3O4 nanocomposite,” Journal of Molecular Liquids, vol. 299, pp. 112167, 2020.

P. Nuengmatcha, S. Chanthai, R. Mahachai, and W. C. Oh, “Sonocatalytic performance of ZnO/graphene/TiO2 nanocomposite for degradation of dye pollutants (methylene blue, texbrite BAC-L, texbrite BBU-L and texbrite NFW-L) under ultrasonic irradiation,” Dyes and Pigments, vol. 134, pp. 487–497, 2016.

R. Nadarajan, W. A. Bakar, R. Ali, and R. Ismail, “Method for polychlorinated biphenyls removal from mussels and its photocatalytic dichlorination,” Applied Catalysis B: Environmental, vol. 218, pp. 327–337, 2017

Y. Chang, C. Wu, H. Wang et al., “Effect of post-heat treatment on the photocatalytic activity of titanium dioxide nanowire membranes deposited on a Ti substrate,” RSC advances, vol. 7, no. 35, pp. 21422–21429, 2017.

L. Lu, R. Shan, Y. Shi, S. Wang, and H. Yuan, “A novel TiO2/biochar composite catalysts for photocatalytic degradation of methyl orange” Chemosphere, vol. 222, pp. 391–398, 2019.

E. García-Ramírez, M. Mondragon-Chaparro, and O. Zelaya-Angel, “Band gap coupling in photocatalytic activity in ZnO–TiO2 thin films,” Applied Physics A, vol. 108, no. 2, pp. 291–297, 2012.

E. M. Sadek, N. A. Mansour, S. M. Ahmed, S. L. Abd-El-Messieh, and D. El-Komy, “Synthesis, characterization, and applications of poly (vinyl chloride) nanocomposites loaded with metal oxide nanoparticles,” Polymer Bulletin, pp. 1–22, 2020.

M. Hasan, A.N. Banerjee, and M. Lee, “Enhanced thermo-mechanical performance and strain-induced band gap reduction of TiO2@PVC nanocomposite films,” Bulletin of Materials Science, vol. 38, no. 2, pp. 283–290, 2015.

T. Uma, T. Mahalingam, and U. Stimming, “Conductivity and thermal studies of solid polymer electrolytes prepared by blending polyvinylchloride, polymethylmethacrylate and lithium sulfate,” Materials Chemistry and Physics, vol. 85, no. 1, pp. 131–136, 2004.

D. X. Vargas, J. R. De la Rosa, C. J. Lucio-Ortiz et al., “Photocatalytic degradation of trichloroethylene in a continuous annular reactor using Cu-doped TiO2 catalysts by sol–gel synthesis,” Applied Catalysis B: Environmental, vol. 179, pp. 249–261, 2015.

P. D. Shivaramu, A. Patil, M. Murthy, S Tubaki et al., “Magnetic substrate supported ZnO-CuO nanocomposite as reusable photo catalyst for the degradation of organic dye,” Materials Today: Proceedings, vol 4, no. 11, pp. 12314–12320, 2017.

D. Tabb and J. Koenig, “Fourier transform infrared study of plasticized and unplasticized poly (vinyl chloride),” Macromolecules, vol. 8, no. 6, pp. 929–934, 1975.

A. Jagadeesan, M. Sasikumar, R. H. Krishna et al., “High electrochemical performance of nano TiO2 ceramic filler incorporated PVC-PEMA composite gel polymer electrolyte for Li-ion battery applications,” Materials Research Express, vol. 6, no. 10, pp. 105524, 2019.

S. Ramesh, K. H. Leen, K. Kumutha, and A. K. Arof, “FTIR studies of PVC/PMMA blend based polymer electrolytes,” Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol. 66, no. 4, pp. 1237–1242, 2007.

X. Zhao, C. Peng, and J. You, “Plasma-Sprayed ZnO/TiO2 Coatings with Enhanced Biological Performance,” Journal of Thermal Spray Technology, vol. 26, no. 6, pp. 1301–1307, 2017.

A. Behboudi, Y. Jafarzadeh, and R. Yegani, “Preparation and characterization of TiO2 embedded PVC ultrafiltration membranes,” Chemical engineering research and design, vol. 114, pp. 96–107, 2016.

T. Ahmad, C. Guria, and A. Mandal, “Synthesis, characterization, and performance studies of mixed-matrix poly (vinyl chloride)-bentonite ultrafiltration membrane for the treatment of saline oily wastewater,” Process Safety and Environmental Protection, vol. 116, pp. 703–717, 2018.

X. Wei, Z. Yang, S. L. Tay, and W. Gao, “Photocatalytic TiO2 nanoparticles enhanced polymer antimicrobial coating,” Applied surface science, vol. 290, pp. 274–279, 2014.

B. I. Stefanov, G. A. Niklasson, C. G. Granqvist, and L. Österlund, “Gas-phase photocatalytic activity of sputter-deposited anatase TiO2 films: Effect of <001> preferential orientation, surface temperature and humidity,” Journal of Catalysis, vol. 335, pp. 187–196, 2016.

M. Lackhoff and R. Niessner, “Photocatalytic atrazine degradation by synthetic minerals, atmospheric aerosols, and soil particles,” Environmental science & technology, vol. 36, no. 24, pp. 5342–5347, 2002.

M. Gholami, M Shirzad-Siboni, M. Farzadkia, and J. K. Yang, “Synthesis, characterization, and application of ZnO/TiO2 nanocomposite for photocatalysis of a herbicide (Bentazon),” Desalination and water treatment, vol. 57, no. 29, pp. 13632–13644, 2016.

M. Gholami, M Shirzad-Siboni, M. Farzadkia, and J. K. Yang, “Study of the decomposition and detoxification of the herbicide bentazon by heterogeneous photocatalysis: Kinetics, intermediates, and transformation pathways,” Applied Catalysis B: Environmental, vol. 200, pp. 150–163, 2017.

A. B. Prevot, E. Pramauro, and M. De la Guardian, “Photocatalytic degradation of carbaryl in aqueous TiO2 suspensions containing surfactants, Chemosphere, vol. 39, no. 3, pp. 493–502, 1999.

N. Vela, J. Fenoll, I. Garrido et al., “Photocatalytic mitigation of triazinone herbicide residues using titanium dioxide in slurry photoreactor,” Catalysis Today, vol. 252, pp. 70–77, 2015.

A. Adak, I. Das, B. Mondal et al., “Degradation of 2,4-dichlorophenoxyacetic acid by UV 253.7 and UV-H2O2: Reaction kinetics and effects of interfering substances,” Emerging Contaminants, vol. 5, pp. 53–60, 2019.

E. P. Melián, O. G. Díaz, J. D. Rodríguez, J. Araña, and J. P. Peña, “Adsorption and photocatalytic degradation of 2,4-dichlorophenol in TiO2 suspensions. Effect of hydrogen peroxide, sodium peroxodisulphate and ozone,” Applied Catalysis A: General, vol. 455, pp. 227–233, 2013.

E. Kanchanatip, N. Grisdanurak, R. Thongruang, and A. Neramittagapong, “Degradation of paraquat under visible light over fullerene modified V-TiO2,” Reaction Kinetics, Mechanisms and Catalysis, vol. 103, no. 1, pp. 227–237, 2011.

N. A. Eleburuike, W. A. Bakar, R. Ali, and M. F. Omar, “Photocatalytic degradation of paraquat dichloride over CeO2-modified TiO2 nanotubes and the optimization of parameters by response surface methodology,” RSC Advances, vol. 6, no. 106, pp. 104082–104093, 2016.

J. Yang, Q. Wu, S. He et al., “Completely <001> oriented anatase TiO2 nanoarrays: topotactic growth and orientation-related efficient photocatalysis,” Nanoscale, vol. 7, no. 33, pp. 13888–13897, 2015.

D. Karimipourfard, R. Eslamloueyan, and N. Mehranbod, “Heterogeneous degradation of stabilized landfill leachate using persulfate activation by CuFe2O4 nanocatalyst: an experimental investigation,” Journal of Environmental Chemical Engineering, vol. 8, no. 2, pp. 103426, 2020