Hydrothermal preparation of CuS2-Cu2O decorated TiO2 for highly efficient activation of peroxymonosulfate to degrade chloroquine phosphate

Wang Yuyao; Wang Dawei; Sirapassorn Kiatphuengporn; Paweena Prapainainar; Anusorn Seubsai

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Hydrothermal preparation of CuS₂-Cu₂O decorated TiO₂ for highly efficient activation of peroxymonosulfate to degrade chloroquine phosphate

Updated：2026-09-17

- Hydrothermal preparation of CuS₂-Cu₂O decorated TiO₂ for highly efficient activation of peroxymonosulfate to degrade chloroquine phosphate
- Chinese Journal of Chemical Engineering Vol. 95, Issue 7, Pages: 80-89(2026)
- Affiliations：
  
  Thailand Advanced Institute of Science and Technology and Institute of Science Tokyo (TAIST-Science Tokyo), Kasetsart University, Bangkok 10900, Thailand
  College of Materials and Chemical Engineering, Southwest Forestry University, Kunming 650224, China
  National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Pathum Thani 12120, Thailand
  Department of Chemical Engineering, Faculty of Engineering, Kasetsart University, Bangkok 10900, Thailand
- Author bio：
  
  *Corresponding author. E-mail address:fengasn@ku.ac.th(A. Seubsai).
- Funds：
- DOI：
  CLC：
- Received：24 October 2025，
  
  Revised：2026-01-13，
  
  Accepted：16 January 2026，
  
  Online First：08 April 2026，
  
  Published：2026-07
- Accepted：
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Wang Yuyao, Wang Dawei, Sirapassorn Kiatphuengporn, et al. Hydrothermal preparation of CuS₂-Cu₂O decorated TiO₂ for highly efficient activation of peroxymonosulfate to degrade chloroquine phosphate[J]. Chinese Journal of Chemical Engineering, 2026, 95(7): 80-89.
DOI：

Wang Yuyao, Wang Dawei, Sirapassorn Kiatphuengporn, et al. Hydrothermal preparation of CuS₂-Cu₂O decorated TiO₂ for highly efficient activation of peroxymonosulfate to degrade chloroquine phosphate[J]. Chinese Journal of Chemical Engineering, 2026, 95(7): 80-89. DOI：

摘要

Abstract

Surface modification of titanium dioxide (TiO

) with transition metals is a feasible solution to enhance its ability to activate peroxymonosulfate (PMS) for environmental remediation. In this study

a novel composite catalyst comprising nano-CuS

and Cu

O decorated anatase-TiO

(CuS

-Cu

O/TiO

) was successfully synthesized

via

a hydrothermal method using thiourea as the sulfur source. The CuS

-Cu

O/TiO

catalyst exhibited excellent performance for the degradation of chloroquine phosphate (CQ) through a photo-assisted PMS activation process

achieving 99% removal efficiency within 10 min under UV irradiation. The effects of PMS dosage and solution pH on CQ degradation were investigated in detail. Mechanism studies

including active species quenching experiments

electron paramagnetic resonance (EPR)

and electrochemical analysis

revealed that the redox cycling of Cu

/Cu

within the CuS

-Cu

O domains and the efficient photo-induced electron transfer derived from TiO

are the key steps in PMS activating. Reactive species

such as photogenerated holes (h+)

hydroxyl radicals (·OH)

and singlet oxygen (

) played essential roles in the oxidative degradation of CQ. Furthermore

liquid chromatography—mass spectrometry (LC—MS) analysis enabled the identification of intermediate products

based on which two plausible degradation pathways of CQ were proposed. This work demonstrates the feasibility of photo-assisted PMS activation for the removal of pharmaceutical pollutants and provides insights into the rational design of TiO

-based composite photocatalysts for wastewater treatment.

关键词

Keywords

references

W.Q. Yang, J. Li, Z.L. Yao, M. Li, A review on the alternatives to antibiotics and the treatment of antibiotic pollution: current development and future prospects, Sci. Total Environ. 926 (2024) 171757.

J. He, T. Feng, L. Tao, Y.E. Peng, L. Tong, X.W. Zhao, X. Shao, L.Y. Xu, Y.L. Yang, Y.B. Zhao, Distribution and impacts on the geological environment of antiviral drugs in major waters of Wuhan, China, China Geol. 5 (3) (2022) 402—410.

S.C. Hu, S.B. Fang, J. Zhao, G.W. Wang, W.X. Qi, G. Zhang, C.R. Huang, J.H. Qu, H.J. Liu, Toxicity evaluation and effect-based identification of chlorine disinfection products of the anti-COVID-19 drug chloroquine phosphate, Environ. Sci. Technol. 57 (21) (2023) 7913—7923.

M.T. Ferreira, C. dos Santos Carvalho, Chloroquine and hydroxychloroquine in the environment and aquatic organisms: a review, Rev. Ambient. Água 18 (2023) 1—24.

W.M. Xiang, F.H. Xu, D. Wan, X. Wang, F. Luo, Y. Chen, Mechanistic investigation of direct photodegradation of chloroquine phosphate under simulated sunlight, Chemosphere 335 (2023) 139093.

H. Rodríguez-Serin, A. Gamez-Jara, M. De La Cruz-Noriega, S. Rojas-Flores, M. Rodriguez-Yupanqui, M. Gallozzo Cardenas, J. Cruz-Monzon, Literature review: evaluation of drug removal techniques in municipal and hospital wastewater, Int. J. Environ. Res. Publ. Health 19 (20) (2022) 13105.

N.H. Othman, N.H. Alias, N.S. Fuzil, F. Marpani, M.Z. Shahruddin, C.M. Chew, K.M. David Ng, W.J. Lau, A.F. Ismail, A review on the use of membrane technology systems in developing countries, Membranes 12 (1) (2022) 30.

A. Khalidi-Idrissi, A. Madinzi, A. Anouzla, A. Pala, L. Mouhir, Y. Kadmi, S. Souabi, Recent advances in the biological treatment of wastewater rich in emerging pollutants produced by pharmaceutical industrial discharges, Int. J. Environ. Sci. 20 (10) (2023) 11719—11740.

N. Parveen, S. Chowdhury, S. Goel, Environmental impacts of the widespread use of chlorine-based disinfectants during the COVID-19 pandemic, Environ. Sci. Pollut. Res. 29 (57) (2022) 85742—85760.

F. Jesus, E. Domingues, C. Bernardo, J.L. Pereira, R.C. Martins, J. Gomes, Ozonation of selected pharmaceutical and personal care products in secondary effluent: degradation kinetics and environmental assessment, Toxics 10 (12) (2022) 765.

P.K. Pandis, C. Kalogirou, E. Kanellou, C. Vaitsis, M.G. Savvidou, G. Sourkouni, A.A. Zorpas, C. Argirusis, Key points of advanced oxidation processes (AOPs) for wastewater, organic pollutants and pharmaceutical waste treatment: a mini review, ChemEngineering 6 (1) (2022) 8.

A. Pattnaik, J.N. Sahu, A.K. Poonia, P. Ghosh, Current perspective of nanoengineered metal oxide based photocatalysts in advanced oxidation processes for degradation of organic pollutants in wastewater, Chem. Eng. Res. Des. 190 (2023) 667—686.

C.C. Dong, W.Z. Fang, Q.Y. Yi, J.L. Zhang, A comprehensive review on reactive oxygen species (ROS) in advanced oxidation processes (AOPs), Chemosphere 308 (2022) 136205.

S.O. Ganiyu, C.A. Martínez-Huitle, M.A. Oturan, Electrochemical advanced oxidation processes for wastewater treatment: advances in formation and detection of reactive species and mechanisms, Curr. Opin. Electrochem. 27 (2021) 100678.

H.J. Li, Y.H. Fu, M. Wang, L. Dong, N. Liu, Comparison study on FeS-activated peroxymonosulfate, persulfate, and hydrogen peroxide for allura red AC decoloration, Environ. Eng. Sci. 40 (10) (2023) 449—459.

M. Collivignarelli, R. Pedrazzani, S. Sorlini, A. Abbaˋ, G. Bertanza, H 2 O 2 based oxidation processes for the treatment of real high strength aqueous wastes, Sustainability 9 (2) (2017) 244.

W.B. Xu, D.L. Huang, G.F. Wang, W. Zhou, L. Du, R.H. Xiao, R.J. Li, H. Huang, Y. Lei, Generation, function and identification of O 2 ·- in persulfate-based advanced oxidation process for pollutants degradation, Chem. Eng. J. 49 9 (2024) 156245.

W. Ren, C. Cheng, P.H. Shao, X.B. Luo, H. Zhang, S.B. Wang, X.G. Duan, Origins of electron-transfer regime in persulfate-based nonradical oxidation processes, Environ. Sci. Technol. 56 (1) (2022) 78—97.

X.M. Peng, J.Q. Wu, Z.L. Zhao, X. Wang, H.L. Dai, Y. Wei, G.P. Xu, F.P. Hu, Activation of peroxymonosulfate by single atom Co-N-C catalysts for highefficient removal of chloroquine phosphate via non-radical pathways:electron-transfer mechanism, Chem. Eng. J. 429 (2022) 132245.

Y.H. Deng, P. Gao, L. Wang, Y.Q. Zhang, J.C. Fu, R.F. Huang, S.F. Zhao, G.Z. Wang, Y.C. Wei, S.Q. Zhou, Activation of peroxymonosulfate by MnO 2 with oxygen vacancies: degradation of organic compounds by electron transfer nonradical mechanism, J. Environ. Chem. Eng. 10 (3) (2022) 107481.

S.Q. Li, J. Yang, K.W. Zheng, S.L. He, Z.G. Liu, S. Song, T. Zeng, Effective activation of peroxymonosulfate by oxygen vacancy induced Musa basjoo biochar to degrade sulfamethoxazole: efficiency and mechanism, Toxics 12 (4) (2024) 283.

Y.J. Pan, F.Y. Meng, J.X. Bai, B. Song, Q. Cao, Highly efficient peroxymonosulfate activation by CoFe 2 O 4 @attapulgite—biochar composites:degradation properties and mechanism insights, J. Environ. Chem. Eng. 12 (3) (2024) 112579.

Y. Jo, C. Kim, G.H. Moon, J. Lee, T.C. An, W. Choi, Activation of peroxymonosulfate on visible light irradiated TiO 2 via a charge transfer complex path, Chem. Eng. J. 346 (2018) 249—257.

F. Tanos, A. Razzouk, G. Lesage, M. Cretin, M. Bechelany, A comprehensive review on modification of titanium dioxide-based catalysts in advanced oxidation processes for water treatment, ChemSusChem 17 (6) (2024) e202301139.

H.T. Yang, B.B. Yang, W. Chen, J.J. Yang, Preparation and photocatalytic activities of TiO 2 -based composite catalysts, Catalysts 12 (10) (2022) 1263.

J. Rodríguez-Chueca, E. Alonso, D.N. Singh, Photocatalytic mechanisms for peroxymonosulfate activation through the removal of methylene blue: a case study, Int. J. Environ. Res. Publ. Health 16 (2) (2019) 198.

Z.C. Hu, W.Q. Zhang, Z.C. Liu, X.T. Zhang, X.M. Wang, Construction of a CuO/TiO 2 @C S-scheme heterojunction for phenol removal by activated peroxymonosulfate, Environ. Res. 277 (2025) 121564.

X.D. Jiang, J.H. Li, J.S. Li, W.C. Xu, Z. Liu, Visible-light-driven peroxymonosulfate activation for accelerating tetracycline removal using Co-TiO 2 nanospheres, Catalysts 13 (5) (2023) 836.

J. Serafin, R. Bujaldón, J. Sreńscek-Nazzal, A. Kałamaga, E. Gomez, X. Vendrell, A. Serra, Transition metal-doped TiO 2 and CeO 2 photocatalysts modified with Ti 3 C 2 MXene for PMS-driven advanced oxidation of pharmaceutical pollutants, Chem. Eng. J. 524 (2025) 169005.

B. Bouzayani, B. Lomba-Fernández, A. Fdez-Sanromán, S.C. Elaoud, M. Á. Sanromán, Advancements in copper-based catalysts for efficient generation of reactive oxygen species from peroxymonosulfate, Appl. Sci. 14 (17) (2024) 8075.

X.W. Liang, S.P. Yu, B. Meng, X.D. Wang, C.X. Yang, C.Q. Shi, J.N. Ding, Advanced TiO 2 -based photoelectrocatalysis: material modifications, charge dynamics, and environmental—energy applications, Catalysts 15 (6) (2025) 542.

M.A. Castro e Souza, N.F.A. Reis, L. de Souza Batista, I. da Costa César, C. Fernandes, G.A. Pianetti, An easy and rapid spectrophotometric method for determination of chloroquine diphosphate in tablets, Curr. Pharmaceut. Anal. 16 (1) (2019) 5—11.

G. Quinõnes Vélez, D. Soto Nieves, A. Castro Vázquez, V. López-Mejías, Polymorphic control in titanium dioxide particles, Nanoscale Adv. 5 (2) (2023) 425—434.

P.R. Jubu, O.S. Obaseki, D.I. Ajayi, E. Danladi, K.M. Chahrour, A. Muhammad, S. Landi, T. Igbawua, H.F. Chahul, F.K. Yam, Considerations about the determination of optical bandgap from diffuse reflectance spectroscopy using the tauc plot, J. Opt. 53 (5) (2024) 5054—5064.

H.R. Zhang, Y.N. Chen, W.Y. Wang, X.T. Chang, K.Y. He, L. Hou, B. Wang, Y. Zhang, S-doping promoting dual redox cycles in the ACM@S-Cu/Fe 3 O 4 /PMS system under visible light for chloroquine phosphate degradation, J. Taiwan Inst. Chem. Eng. 174 (2025) 106217.

F. Wang, Y. Gao, Y.T. Chai, C.C. Wang, J.F. Wang, X.H. Yi, Y. Li, H.F. Fu, C. Zhao, P. Wang, Interfacial engineering regulating electronic structure of homologous S-scheme Co 3 O 4 @C-TiO 2 heteroju nction for enhanced Fenton-like reaction activity, Appl. Catal. B Environ. Energy 364 (2025) 124848.

P.J. Duan, X.N. Liu, B.H. Liu, M. Akram, Y.W. Li, J.W. Pan, Q.Y. Yue, B.Y. Gao, X. Xu, Effect of phosphate on peroxymonosulfate activation: accelerating generation of sulfate radical and underlying mechanism, Appl. Catal. B Environ. 298 (2021) 120532.

Y.H. Guan, J. Ma, X.C. Li, J.Y. Fang, L.W. Chen, Influence of pH on the formation of sulfate and hydroxyl radicals in the UV/peroxymonosulfate system, Environ. Sci. Technol. 45 (21) (2011) 9308—9314.

X.H. Wang, G.R. Liu, D. Zhang, S. Han, J. Yin, J.T. Jiang, W.P. Wang, Z.C. Li, Ndoped carbon sheets supported P-Fe 3 O 4 -MoO 2 for freshwater and seawater electrolysis, J. Colloid Interface Sci. 652 (2023) 1217—1227.

L.M. Liu, W.Y. Yang, W.Z. Sun, Q. Li, J.K. Shang, Creation of Cu 2 O@TiO 2 composite photocatalysts with p—n heterojunctions formed on exposed Cu 2 O facets, their energy band alignment study, and their enhanced photocatalytic activity under illumination with visible light, ACS Appl. Mater. Interfaces 7 (3) (2015) 1465—1476.

C. Ma, X. Mi, P.P. Li, Z.G. He, H.Q. Wang, Photo-assisted oxygen-rich vacancy copper oxide catalyst to activate peroxymonosulfate (PMS) for efficient degradation of fulvic acid, J. Water Process Eng. 66 (2024) 106060.

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