Engineering Photocatalytic TiO₂/CuWO₄ Coatings: The Synergistic Effect of Oxidants on Heavy Metal Remediation

Document Type : Research Paper

Authors

Bu-Ali Sina University, Department of Materials Engineering, Faculty of Engineering, Hamedan, Iran

10.22059/jufgnsm.2025.02.03

Abstract

A highly active TiO₂/CuWO₄ heterostructure coating for Cr⁶⁺ photoreduction was developed through PEO and hydrothermal post-treatment. Characterizations such as FESEM, GXRD, AFM and wettability, revealed that nano-sized CuWO₄ integration transforms the morphology, producing a hierarchical, microporous base with uniformly distributed particles and a super-hydrophilic, rough surface for improved accessibility. Oxidant screening revealed that both radical (〖SO〗_4^(⦁-), 〖HO〗^⦁) and non-radical species are critical to the mechanism. Peroxydisulfate (PDS) achieved the highest synergy (synergistic factor= 0.9) via sulfate radical generation, significantly outperforming peroxymonosulfate (PMS) and the ineffective H₂O₂. This study proposes a dual-pathway mechanism and introduces a durable, scalable photocatalytic coating solution for environmental cleanup.

Keywords

References

  1. R. Chaharmahali, A. Fattah-alhosseini, M. Karbasi, D. Dastan, S. Giannakis, Synergistic effects of PEO and hydrothermal post-treatment on the photocatalytic behavior of TiO₂/Bi₂WO₆ coatings: Distinguishing between Type II and Z-Scheme heterojunctions, J. Environ. Chem. Eng. 13 (2025) 116583.
  2. R. Chaharmahali, A. Fattah-alhosseini, M. Karbasi, Unveiling enhanced photocatalytic behavior: Plasma electrolytic oxidation for TiO2/Bi2WO6 heterojunction coatings to enhance the photocatalytic degradation of methylene blue under visible light, Ceram. Int. 51 (2025) 11255–11266.
  3. S.J. McGrane, Impacts of urbanisation on hydrological and water quality dynamics, and urban water management: a review, Hydrol. Sci. J. 61 (2016) 2295–2311.
  4. A. Fattah-alhosseini, M. Karbasi, H. Bahramian, A thorough investigation of the utilization of metal-organic framework (MOF) coated titanium dioxide in photocatalytic applications: A review, Appl. Surf. Sci. Adv. 18 (2023) 100504.
  5. L.B. Khalil, W.E. Mourad, M.W. Rophael, Photocatalytic reduction of environmental pollutant Cr(VI) over some semiconductors under UV/visible light illumination, Appl. Catal. B Environ. 17 (1998) 267–273.
  6. D. Zhu, Q. Zhou, Action and mechanism of semiconductor photocatalysis on degradation of organic pollutants in water treatment: A review, Environ. Nanotechnology, Monit. Manag. 12 (2019) 100255.
  7. Y. Cai, H. Shu, F. Yu, Y. Yang, Molecular sieving of semiconductive NTU-9 coatings on titanium dioxide nanowire arrays: Augmented yet selective photoelectrochemical response enabled by boosting charge separation and transfer in confined space, J. Colloid Interface Sci. 630 (2023) 523–533.
  8. P. He, J. Zhu, Y. Chen, F. Chen, J. Zhu, M. Liu, K. Zhang, M. Gan, Pyrite-activated persulfate for simultaneous 2,4-DCP oxidation and Cr(VI) reduction, Chem. Eng. J. 406 (2021) 126758.
  9. S. Stojadinović, N. Tadić, N. Radić, B. Grbić, R. Vasilić, CdS particles modified TiO2 coatings formed by plasma electrolytic oxidation with enhanced photocatalytic activity, Surf. Coatings Technol. 344 (2018) 528–533.
  10. J. Wu, X. Jiang, Y. Zhang, Q. Fu, C. Pan, Preparation of high-concentration substitutional carbon-doped TiO2 film via a two-step method for high-performance photocatalysis, RSC Adv. 8 (2018) 36691–36696.
  11. Y.Q. Wang, X.D. Jiang, C.X. Pan, In Situ Preparation of TiO2 Composite Layer upon Ti Alloy Substrate Using Micro-Arc Oxidation and its Photocatalytic Property, Mater. Sci. Forum 663–665 (2010) 3–11.
  12. M.S. Sharifiyan, A. Fattah-alhosseini, M. Karbasi, Photocatalytic evaluation of hierarchical TiO2/WO3 hybrid coating created by PEO/hydrothermal method, Appl. Surf. Sci. Adv. 18 (2023) 100541.
  13. H. Bahramian, A. Fattah-alhosseini, M. Karbasi, E. Nikoomanzari, S. Giannakis, Synergy of Cu2+-Cu(OH)2-CuO with TiO2 coatings, fabricated via plasma electrolytic Oxidation: Insights into the multifaceted mechanism governing visible light-driven photodegradation of tetracycline, Chem. Eng. J. 476 (2023) 146588.
  14. P. Raizada, S. Sharma, A. Kumar, P. Singh, A.A. Parwaz Khan, A.M. Asiri, Performance improvement strategies of CuWO4 photocatalyst for hydrogen generation and pollutant degradation, J. Environ. Chem. Eng. 8 (2020) 104230.
  15. H. Salimi, A. Fattah-alhosseini, M. Karbasi, E. Nikoomanzari, Development of WO3-incorporated porous ceramic coating: A key role of WO3 nanoparticle concentration on methylene blue photodegradation upon visible light illumination, Ceram. Int. 49 (2023) 32181–32192.
  16. E. Nikoomanzari, M. Karbasi, W. C.M.A. Melo, H. Moris, K. Babaei, S. Giannakis, A. Fattah-alhosseini, Impressive strides in antibacterial performance amelioration of Ti-based implants via plasma electrolytic oxidation (PEO): A review of the recent advancements, Chem. Eng. J. 441 (2022) 136003.
  17. R. Hosseini, A. Fattah-alhosseini, M. Karbasi, Photodegradation of tetracycline using surface oxygen vacancy-enriched PEO coating under visible light, Surfaces and Interfaces 42 (2023) 103311.
  18. M. Kaseem, S. Fatimah, N. Nashrah, Y.G. Ko, Recent progress in surface modification of metals coated by plasma electrolytic oxidation: Principle, structure, and performance, Prog. Mater. Sci. 117 (2021) 100735.
  19. M.S. Sharifiyan, A. Fattah-alhosseini, M. Karbasi, Optimizing the hydrothermal post-treatment process for a TiO2/WO3 hybrid coating to enhance the photocatalytic degradation of methylene blue under visible light, Ceram. Int. 49 (2023) 35175–35185.
  20. H. Bahramian, A. Fattah-alhosseini, M. Karbasi, M. Kaseem, M. Sillanpää, B. Dikici, Influence of CuWO₄-induced heterostructures on porous TiO₂ ceramic coatings for Cr6+ reduction, Process Saf. Environ. Prot. 202 (2025) 107814.
  21. A. Saberyoun, A. Fattah-alhosseini, M. Karbasi, R. Hosseini, M. Kaseem, Boosting the visible-light-driven photocatalytic efficiency in porous Cu/TiO2 ceramic coatings, Ceram. Int. 50 (2024) 31313–31325.
  22. T.T. My Hang, N.H. Thao Vy, N.T. Hanh, T.-D. Pham, L.T. Hoang Yen, Facile synthesis of copper tungstate (CuWO4) for novel photocatalytic degradation of tetracycline under visible light, Sustain. Chem. Pharm. 21 (2021) 100407.
  23. A. Santos-Coquillat, M. Mohedano, E. Martinez-Campos, R. Arrabal, A. Pardo, E. Matykina, Bioactive multi-elemental PEO-coatings on titanium for dental implant applications, Mater. Sci. Eng. C 97 (2019) 738–752.
  24. A. Fattah-Alhosseini, M.K. Keshavarz, M. Molaei, S.O. Gashti, Plasma Electrolytic Oxidation (PEO) Process on Commercially Pure Ti Surface: Effects of Electrolyte on the Microstructure and Corrosion Behavior of Coatings, Metall. Mater. Trans. A 49 (2018) 4966–4979.
  25. W. Thongsuwan, T. Kumpika, P. Singjai, Effect of high roughness on a long aging time of superhydrophilic TiO2 nanoparticle thin films, Curr. Appl. Phys. 11 (2011) 1237–1242.
  26. J. Wang, S. Wang, Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants, Chem. Eng. J. 334 (2018) 1502–1517.
  27. X. Duan, H. Sun, Z. Shao, S. Wang, Nonradical reactions in environmental remediation processes: Uncertainty and challenges, Appl. Catal. B Environ. 224 (2018) 973–982.
  28. P. Hu, M. Long, Cobalt-catalyzed sulfate radical-based advanced oxidation: A review on heterogeneous catalysts and applications, Appl. Catal. B Environ. 181 (2016) 103–117.
  29. X. Zhou, Q. Zhao, J. Wang, Z. Chen, Z. Chen, Nonradical oxidation processes in PMS-based heterogeneous catalytic system: Generation, identification, oxidation characteristics, challenges response and application prospects, Chem. Eng. J. 410 (2021) 128312.
  30. Y. Peng, H. Tang, B. Yao, X. Gao, X. Yang, Y. Zhou, Activation of peroxymonosulfate (PMS) by spinel ferrite and their composites in degradation of organic pollutants: A Review, Chem. Eng. J. 414 (2021) 128800.
  31. W.-M. Yang, F. Liu, Y.-T. Jin, Z.-M. Dong, G.-C. Zhao, Efficient Reduction of Cr(VI) with Carbon Quantum Dots, ACS Omega 7 (2022) 23555–23565.
  32. S. Mohammadi, G. Moussavi, S. Shekoohiyan, M.L. Marín, F. Boscá, S. Giannakis, A continuous-flow catalytic process with natural hematite-alginate beads for effective water decontamination and disinfection: Peroxymonosulfate activation leading to dominant sulfate radical and minor non-radical pathways, Chem. Eng. J. 411 (2021).
  33. C. Zhu, Y. Zhang, Z. Fan, F. Liu, A. Li, Carbonate-enhanced catalytic activity and stability of Co3O4 nanowires for 1O2-driven bisphenol A degradation via peroxymonosulfate activation: Critical roles of electron and proton acceptors, J. Hazard. Mater. 393 (2020) 122395.
  34. R. Hosseini, A. Fattah-alhosseini, M. Karbasi, S. Giannakis, Tailoring surface defects in Plasma Electrolytic Oxidation (PEO) treated 2-D black TiO2: Post-treatment role, and intensification by peroxymonosulfate activation in visible light-driven photocatalysis, Appl. Catal. B Environ. 340 (2024) 123197.
  35. A.D. Bokare, W. Choi, Advanced Oxidation Process Based on the Cr(III)/Cr(VI) Redox Cycle, Environ. Sci. Technol. 45 (2011) 9332–9338.
Journal of Ultrafine Grained and Nanostructured Materials
Volume 58, Issue 2
December 2025
Pages 152-160

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History

  • Receive Date: 11 November 2025
  • Revise Date: 22 November 2025
  • Accept Date: 23 November 2025

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