Document Type : Research Paper

Authors

Department of Chemical Engineering, Faculty of Interdisciplinary Sciences and Technologies, University of Bonab, Bonab, Iran.

Abstract

In this study, 5 wt. %Cu-doped TiO₂ nanoparticles (NPs) were synthesized through a green and sustainable method, utilizing Cannabis sativa leaf extract as a reducing agent to promote eco-friendly wastewater treatment. The NPs were characterized using XRD, FESEM, BET, EDAX, and TEM, revealing uniform dispersion, an average particle size of approximately 20.5 nm, and a high surface area of 92 m²/g. These NPs were employed for adsorption of Methylene Blue (MB) and Rhodamine B (RhB) dyes from aqueous solutions at initial concentrations of 1–10 mg/L. Adsorption experiments, conducted over 150 min, showed equilibrium data best fitting the Freundlich isotherm (R² = 0.9979 for MB, 0.9995 for RhB), indicating multilayer adsorption. Kinetic studies confirmed that the Elovich models provided the best fit (R² > 0.997), suggesting chemisorption-dominated processes. The NPs exhibited high adsorption efficiency, offering a cost-effective and sustainable solution for treating textile wastewater, addressing critical environmental challenges posed by industrial dyes.

Keywords

Abbasi, B. et al. (2018) 'Biogenic synthesis of Au, Ag and Au–Ag alloy nanoparticles using Cannabis sativa leaf extract', IET Nanobiotechnol., 12 (3), pp. 277-284. doi: https://doi.org/10.1049/iet-nbt.2017.0169
Abisharani, J. M. et al. (2020) 'Influence of 2,4-Diamino-6-Phenyl-1-3-5-triazine on bio synthesized TiO2 dye-sensitized solar cell fabricated using poly (ethylene glycol) polymer electrolyte', Materials Research Express, 7 (2), p. 025507. doi: https://doi.org/10.1088/2053-1591/ab7066
Adamu, A., et al. (2023) 'Investigation of Cu/TiO2 synthesis methods and conditions for CO2 photocatalytic reduction via conversion of bicarbonate/carbonate to formate', Journal of CO2 Utilization, 70, p. 102428. doi: https://doi.org/10.1016/j.jcou.2023.102428
Aguilar, T., et al. (2013) 'A route for the synthesis of Cu-doped TiO2 nanoparticles with a very low band gap', Chemical Physics Letters, 571, pp. 49-53. doi: https://doi.org/10.1016/j.cplett.2013.04.007
Ahlawat, W., et al. (2020) 'Carbonaceous nanomaterials as effective and efficient platforms for removal of dyes from aqueous systems', Environmental Research, 181, p. 108904. doi: https://doi.org/10.1016/j.envres.2019.108904
Ahmad, M. M. et al. (2021) 'Investigation of TiO2 Nanoparticles synthesized by sol-gel method for effectual photodegradation, Oxidation and Reduction Reaction', Crystals, 11(12). doi: https://doi.org/10.3390/cryst11121456.
Ahmad, N. et al. (2023) 'Insight into the adsorption thermodynamics, kinetics, and photocatalytic studies of polyaniline/SnS2 nanocomposite for dye removal', Journal of Hazardous Materials Advances, 10, p. 100321. doi: https://doi.org/10.1016/j.hazadv.2023.100321
Aksakal, O. and Ucun, H. (2010) 'Equilibrium, kinetic and thermodynamic studies of the biosorption of textile dye (Reactive Red 195) onto Pinus sylvestris L', Journal of Hazardous Materials, 181 (1), pp. 666-672. doi: https://doi.org/10.1016/j.jhazmat.2010.05.064
Al-Assaly, R. et al. (2024) 'Antimicrobial performance and instrumental analysis for hexagonal ZnO NPs biosynthesized via Ziziphus leaf extract', Oxford Open Materials Science, 4 (1), itae011. doi: https://doi.org/10.1093/oxfmat/itae011
An, B. (2020) 'Cu(II) and As(V) Adsorption Kinetic Characteristic of the Multifunctional Amino Groups in Chitosan', Processes, 8(9), p. 1194. doi: https://doi.org/10.3390/pr8091194.
Baratta, M., Nicoletta, F. P. and De Filpo, G. (2025) 'Graphene Oxide-Doped CNT Membrane for Dye Adsorption', Nanomaterials, 15 (11), p. 782. doi: https://doi.org/doi:10.3390/nano15110782
Belachew, N., et al. (2021) 'Synthesis of amino acid functionalized Fe3O4 nanoparticles for adsorptive removal of Rhodamine B', Applied Water Science, 11, p. 33. doi: https://doi.org/10.1007/s13201-021-01371-y
Benhadj, M., et al. (2023) 'Wheat Straw-Derived Activated Carbon for Efficient Removal of Methylene blue: Kinetics, Thermodynamics, and Adsorption Mechanism', Key Engineering Materials, 954, pp. 73-93. doi: https://doi.org/10.4028/p-6CKBMf
BinSabt, M., et al. (2022) 'Green Synthesis of CS-TiO2 NPs for efficient photocatalytic degradation of methylene blue dye', Polymers, 14 (13), p. 2677. doi: https://doi.org/10.3390/polym14132677
Bopape, D. A., Ntsendwana, B. and Mabasa, F. D. (2024) 'Photocatalysis as a pre-discharge treatment to improve the effect of textile dyes on human health: A critical review', Heliyon, 10 (20), p. e39316. doi: https://doi.org/10.1016/j.heliyon.2024.e39316
Cheng, H., et al. (2014) 'Effect of phase composition, morphology, and specific surface area on the photocatalytic activity of TiO2 nanomaterials', RSC Advances, 4 (87), pp. 47031-47038. doi: https://doi.org/10.1039/C4RA05509H
Cheung, C. W., Porter, J. F. and McKay, G. (2000) 'Elovich equation and modified second-order equation for sorption of cadmium ions onto bone char', Journal of Chemical Technology & Biotechnology, 75 (11), pp. 963-970. Available at: https://doi.org/10.1002/1097-4660(200011)75:11%3C963::AID-JCTB302%3E3.0.CO;2-Z (Acccessed date: 21 May 2025 ).
Chiani, E., et al. (2020) 'Adsorption of cationic dye from aqueous solution using SBA-15 nano particles synthesized by stem sweep ash as the source of silica', Journal of Applied Research in Water and Wastewater, 7 (2), pp. 172-179. doi: https://doi.org/10.22126/arww.2021.5648.1186
Chu, K. H. (2021) 'Revisiting the Temkin Isotherm: Dimensional inconsistency and approximate forms', Industrial & Engineering Chemistry Research, 60 (35), pp. 13140-13147. doi: https://doi.org/10.1021/acs.iecr.1c01788
Csakvari, A. C., et al. (2021) 'Green synthesis, characterization, and antibacterial properties of silver nanoparticles obtained by using diverse varieties of cannabis sativa leaf extracts', Molecules, 26 (13), p. 4041. doi: https://doi.org/doi:10.3390/molecules26134041
Dada, A. O. et al. (2012) 'Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms studies of equilibrium sorption of Zn2+ unto phosphoric acid modified rice husk', IOSR Journal of Applied Chemistry, 3 (1), pp. 38-45. doi: https://doi.org/10.9790/5736-0313845.
Deliza, D. et al. (2025) 'Green synthesis approach on fabrication of TiO2 nanoparticle using peel extract of Baccaurea racemosa for photocatalytic degradation of Acid Red-185', Environmental Nanotechnology, Monitoring & Management, 23, p. 101074. doi: https://doi.org/10.1016/j.enmm.2025.101074
Dutta, S. et al. (2024) 'Contamination of textile dyes in aquatic environment: Adverse impacts on aquatic ecosystem and human health, and its management using bioremediation', Journal of Environmental Management, 353, p. 120103. doi: https://doi.org/10.1016/j.jenvman.2024.120103
Eddy, D. R. et al. (2024) 'A review of recent developments in green synthesis of TiO2 nanoparticles using plant extract: Synthesis, characterization and photocatalytic activity', Inorganic Chemistry Communications, 165, p. 112531. doi: https://doi.org/10.1016/j.inoche.2024.112531
Gadge, A. S. et al. (2025) 'Novel green synthesis of Gd-doped TiO2 nanoparticles for environmental remediation: statistical modeling and process optimization', New Journal of Chemistry, 49 (14), pp. 5995-6011. doi: https://doi.org/10.1039/D5NJ00856E
Gupta, V. K. et al. (2012) 'Adsorptional photocatalytic degradation of methylene blue onto pectin–CuS nanocomposite under solar light', Journal of Hazardous Materials, 243, pp. 179-186. doi: https://doi.org/10.1016/j.jhazmat.2012.10.018
Habeeb, S. A., Zinatizadeh, A. A. and Zangeneh, H. (2023) 'Photocatalytic Decolorization of Direct Red16 from an Aqueous Solution Using B-ZnO/TiO2 Nano Photocatalyst: Synthesis, Characterization, Process Modeling, and Optimization', Water, 15 (6), p. 1203. doi: https://doi.org/10.3390/w15061203
Ho, D. Q. et al. (2025) 'Green Synthesis of TiO2-CeO2 nanocomposites using plant extracts for efficient organic dye photodegradation', Catalysts, 15 (6), p. 583. doi: https://doi.org/10.3390/catal15060583
Hosseinzadeh, G. et al. (2024) 'Construction of PVC/PVA WO3 3D nanostructure thin film nanocomposite for treatment of oil refinery wastewater', Journal of Polymers and the Environment, 32, pp. 1879-1891. doi: https://doi.org/10.1007/s10924-023-03077-5
Jadhav, V. et al. (2025) 'Green synthesis of Ag@TiO2 nanomaterials using Achyranthes aspera leaf extract for sustainable photocatalytic degradation of dyes', Discover Applied Sciences, 7 (7), pp. 732. doi: https://doi.org/10.1007/s42452-025-07324-3
Jaramillo-Fierro, X. and Cuenca, G. (2024) 'Enhancing Methylene Blue Removal through Adsorption and Photocatalysis—A Study on the GO/ZnTiO3/TiO2 Composite', International Journal of Molecular Sciences, 25 (8), p. 4367. doi: https://doi.org/10.3390/ijms25084367
Jayapriya, M. and Arulmozhi, M. (2021) 'Beta vulgaris peel extract mediated synthesis of Ag/TiO2 nanocomposite: Characterization, evaluation of antibacterial and catalytic degradation of textile dyes-an electron relay effect', Inorganic Chemistry Communications, 128, p. 108529. doi: https://doi.org/10.1016/j.inoche.2021.108529
Kasemodel, M. C. et al. (2025) 'The Investigation of the Adsorption of Methylene Blue from Water by Torrefied Biomass', Colorants, 4 (2), p. 21. doi: https://doi.org/10.3390/colorants4020021
Khan, M. A. M. et al. (2022) 'Characterization and photocatalytic performance of hydrothermally synthesized Cu-doped TiO2 NPs', Optical Materials, 133, p. 112983. doi: https://doi.org/10.1016/j.optmat.2022.112983
Khin, M. M. et al. (2012) 'A review on nanomaterials for environmental remediation', Energy & Environmental Science, 5 (8), pp. 8075-8109. doi: https://doi.org/10.1039/C2EE21818F
Kuvarega, A. T. and Mamba, B. B. (2017) 'TiO2-based photocatalysis: toward visible light-responsive photocatalysts through doping and fabrication of carbon-based nanocomposites', Critical Reviews in Solid State and Materials Sciences, 42 (4), pp. 295-346. doi: https://doi.org/10.1080/10408436.2016.1211507
MiarAlipour, S. et al. (2018) 'TiO2/porous adsorbents: Recent advances and novel applications', Journal of Hazardous Materials, 341, pp. 404-423. doi: https://doi.org/10.1016/j.jhazmat.2017.07.070
Molla, A., et al. (2019) 'Selective adsorption of organic dyes on graphene oxide: Theoretical and experimental analysis', Applied Surface Science, 464, pp. 170-177. doi: https://doi.org/10.1016/j.apsusc.2018.09.056
Munyegaju, J. et al. (2022) 'Textile effluent treatment using Avocado seeds based activated carbon', Journal of Applied Research in Water and Wastewater, 9 (1), pp. 83-90. doi: https://doi.org/10.22126/arww.2022.8008.1258
Nabi, G., et al. (2021) 'Green synthesis of spherical TiO2 nanoparticles using Citrus Limetta extract: Excellent photocatalytic water decontamination agent for RhB dye', Inorganic Chemistry Communications, 129, p. 108618. doi: https://doi.org/10.1016/j.inoche.2021.108618
Nagaraj, G. et al. (2021) 'Effects of the surface of solar-light photocatalytic activity of Ag-doped TiO2 nanohybrid material prepared with a novel approach', Applied Physics A, 127, p. 269. doi: https://doi.org/10.1007/s00339-021-04427-7
Nassar, M. Y. et al. (2017) 'MgO nanostructure via a sol-gel combustion synthesis method using different fuels: An efficient nano-adsorbent for the removal of some anionic textile dyes', Journal of Molecular Liquids, 225, pp. 730-740. doi: https://doi.org/10.1016/j.molliq.2016.10.135
Natsir, M., et al. (2021) 'Synthesis and charcterization of Cu-doped TiO2 (Cu/TiO2) nanoparticle as antifungal phytophthora palmivora', Journal of Physics: Conference Series, 1899 (1), p. 012039. doi: https://doi.org/10.1088/1742-6596/1899/1/012039
Nawaz, A. et al. (2023) 'Solar light driven degradation of textile dye contaminants for wastewater treatment - studies of novel polycationic selenide photocatalyst and process optimization by response surface methodology desirability factor', Chemosphere, 328, p. 138476. doi: https://doi.org/10.1016/j.chemosphere.2023.138476
Nayebzadeh, H., Naderi, F. and Rahmanivahid, B. (2021) 'Effect of doping Al cations into MgFe2O4 magnetic structure for efficient removals of methyl orange dye from water', Journal of Inorganic and Organometallic Polymers and Materials, 31 (2), pp. 776-789. doi: https://doi.org/10.1007/s10904-020-01816-y
Osmari, T. A. et al. (2013) 'Statistical analysis of linear and non-linear regression for the estimation of adsorption isotherm parameters', Adsorption Science & Technology, 31 (5), pp. 433-458. doi: https://doi.org/10.1260/0263-6174.31.5.433
Oyetade, O. A. et al. (2015) 'Effectiveness of carbon nanotube–cobalt ferrite nanocomposites for the adsorption of rhodamine B from aqueous solutions', RSC Advances, 5 (29), pp. 22724-22739. doi: https://doi.org/10.1039/C4RA15446K
Pankaj, Sharma, R. and Verma, S. K. (2021) 'Equilibrium, kinetic and mechanism studies on adsorption of textile disperse dye from aqueous solution onto TiO2 in the presence of ultrasound and rare earth ions', Materials Today: Proceedings, 44, pp. 2158-2167. doi: https://doi.org/10.1016/j.matpr.2020.12.279
Piaskowski, K., Świderska-Dąbrowska, R. and Zarzycki, P. K. (2019) 'Dye removal from water and wastewater using various physical, chemical, and biological processes', Journal of AOAC INTERNATIONAL, 101 (5), pp. 1371-1384. doi: https://doi.org/10.5740/jaoacint.18-0051
Rahmanivahid, B., Naderi, F. and Nayebzadeh, H. (2020) 'Removing methyl orange molecules from aqueous medium by magnetic nanoparticles: Evaluating adsorption factors, isotherms, kinetics and thermodynamics', Journal of Water and Environmental Nanotechnology, 5 (1), pp. 1-16. doi: https://doi.org/10.22090/jwent.2020.01.001
Ramesh, A. V. et al. (2018) 'Facile green synthesis of Fe3O4 nanoparticles using aqueous leaf extract of Zanthoxylum armatum DC. for efficient adsorption of methylene blue', Journal of Asian Ceramic Societies, 6 (2), pp. 145-155. doi: https://doi.org/10.1080/21870764.2018.1459335
Ramzan, M. et al. (2021) 'Green synthesis of Cu@TiO2 via cedrus deodara leaf extract: A novel composite with high photocatalytic and antibacterial activity', Current Research in Green and Sustainable Chemistry, 4, p. 100137. doi: https://doi.org/10.1016/j.crgsc.2021.100137
Revellame, E. D. et al. (2020) 'Adsorption kinetic modeling using pseudo-first order and pseudo-second order rate laws: A review', Cleaner Engineering and Technology, 1, p. 100032. doi: https://doi.org/10.1016/j.clet.2020.100032
Sadeghpour, P. et al. (2022) 'Ultrasonic-promoted growth of staggered heterostructured tin(II) oxide nanoparticles on bulk carbon nitride nanolayer: Activated in solar spectrum with enhanced photocatalytic treatment of dyes effluents', Solar Energy, 241, pp. 437-451. doi: https://doi.org/10.1016/j.solener.2022.06.027
Saikia, J. et al. (2013) 'Malachite nanoparticle: A potent surface for the adsorption of xanthene dyes', Journal of Environmental Chemical Engineering, 1 (4), pp. 1166-1173. doi: https://doi.org/10.1016/j.jece.2013.09.002
Saini, R. and Kumar, P. (2023) 'Green synthesis of TiO2 nanoparticles using Tinospora cordifolia plant extract & its potential application for photocatalysis and antibacterial activity', Inorganic Chemistry Communications, 156, p. 111221. doi: https://doi.org/10.1016/j.inoche.2023.111221
Sajjadi, S. M. (2024) 'Evaluation of the various adsorption isotherm models for the photocatalytic removal of methylene blue from the wastewater by graphene oxide/TiO2/SiO2', Journal of Applied Research in Water and Wastewater, 11 (1), pp. 59-66. doi: https://doi.org/10.22126/arww.2023.8980.1286
Sajjadi, S. M. and Etemadi, H. (2025a) 'Effect of Ni/Al2O3 nanoparticles on the antifouling properties of polyvinyl chloride membranes in water treatment', International Journal of Environmental Science and Technology, 22 (10), pp. 9157-9174. doi: https://doi.org/10.1007/s13762-025-06451-z
Sajjadi, S. M., Etemadi, H. and Zaremanesh, M. (2024a) 'Synthesis and evaluation of PVC-Cu/Al2O3 nanocomposite membranes for removing of natural organic matter from the wastewater', Asia-Pacific Journal of Chemical Engineering, 19 (4), p. e3082. doi: https://doi.org/10.1002/apj.3082
Sajjadi, S. M., Fardi Ilkhchy, A. and Aygani, A. (2025b) 'Investigating the efficiency of the ultrasonic-assisted sol-gel synthesized Cu/ZnO photocatalysts in degradation of textile dyes', Materials Chemistry and Physics, 337, p. 130590. doi: https://doi.org/10.1016/j.matchemphys.2025.130590
Sajjadi, S. M., Haghighi, M. and Eshghi, J. (2019) 'Synergic influence of potassium loading and plasma-treatment on anti-coke property of K-Promoted bimetallic NiCoNiAl2O4 nanocatalyst applied in O2-Enhanced dry reforming of CH4', International Journal of Hydrogen Energy, 44 (26), pp. 13397-13414. doi: https://doi.org/10.1016/j.ijhydene.2019.03.260
Sajjadi, S. M. et al. (2022a) 'Various calcium loading and plasma-treatment leading to controlled surface segregation of high coke-resistant Ca-promoted NiCo–NiAl2O4 nanocatalysts employed in CH4/CO2/O2 reforming to H2', International Journal of Hydrogen Energy, 47 (59), pp. 24708-24727. doi: https://doi.org/10.1016/j.ijhydene.2022.05.233
Sajjadi, S. M., Haghighi, M. and Rahmani, F. (2022b) 'On the synergic effect of various anti-coke materials (Ca–K–W) and glow discharge plasma on Ni-based spinel nanocatalyst design for syngas production via hybrid CO2/O2 reforming of methane', Journal of Natural Gas Science and Engineering, 108, p. 104810. doi: https://doi.org/10.1016/j.jngse.2022.104810
Sajjadi, S. M. and Hosseinzadeh, G. (2025c) 'Utilization of green synthesized calcium doped TiO2 photocatalysts for the solar-light-driven degradation of dyes in aqueous solution', Journal of Nanostructures, 15 (2), pp. 684-701. doi: https://doi.org/10.22052/jns.2025.02.027
Sajjadi, S. M. and Hossinzadeh, G. (2024b) 'Textile dyes removing from the wastewater by green synthesized Cu-doped ZnO photocatalysts under the simulated sunlight illumination', Ceramics International, 50 (19, Part B), pp. 36271-36285. doi: https://doi.org/10.1016/j.ceramint.2024.07.011
Shahzadi, T. et al. (2022) 'Eco-friendly synthesis of ZnO nanoparticles using Cannabis sativa and assessment of its activities as efficient dyes removal and antioxidant agent', International Journal of Environmental Analytical Chemistry, 102 (16), pp. 4738-4756. doi: https://doi.org/10.1080/03067319.2020.1789610
Sharma, J. et al. (2022) 'Toxic effects of Rhodamine B on antioxidant system and photosynthesis of Hydrilla verticillata', Journal of Hazardous Materials Letters, 3, pp. 100069. doi: https://doi.org/10.1016/j.hazl.2022.100069
Verma, V., et al. (2022) 'A Review on green synthesis of TiO2 NPs: Photocatalysis and antimicrobial applications', Polymers, 14 (7), p. 1444. doi: https://doi.org/doi:10.3390/polym14071444
Vieira, G. B. et al. (2018) 'CeO2/TiO2 nanostructures enhance adsorption and photocatalytic degradation of organic compounds in aqueous suspension', Journal of Photochemistry and Photobiology A: Chemistry, 353, pp. 325-336. doi: https://doi.org/10.1016/j.jphotochem.2017.11.045
Vimonses, V. et al. (2009) 'Kinetic study and equilibrium isotherm analysis of Congo Red adsorption by clay materials', Chemical Engineering Journal, 148 (2), pp. 354-364. doi: https://doi.org/10.1016/j.cej.2008.09.009
Wang, X. S. and Chen, J. P. (2009) 'Biosorption of Congo Red from aqueous solution using wheat bran and rice bran: batch studies', Separation Science and Technology, 44 (6), pp. 1452-1466. doi: https://doi.org/10.1080/01496390902766132
Wierzbicka, E. et al. (2022) 'Efficient Rhodamine B dye removal from water by acid- and organo-modified halloysites', Minerals, 12 (3), p. 350. doi: https://doi.org/10.3390/min12030350
Yitagesu, G. B., Leku, D. T. and Workneh, G. A. (2023) 'Green synthesis of TiO2 using impatiens rothii hook.f. leaf extract for efficient removal of methylene blue dye', ACS Omega, 8 (46), pp. 43999-44012. doi: https://doi.org/10.1021/acsomega.3c06142
Zhou, J. et al. (2025) 'Study on the adsorption characteristics of methylene blue by magnesium-modified fly ash', Molecules, 30 (5), p. 992. doi: https://doi.org/10.3390/molecules30050992