Sonochemical synthesis and catalytic activity of the composite of Cu2O–clinoptilolite nanoparticle

Keywords

synthesis, ultrasonic cavitation, clinoptilolite, Cu₂O nanoparticles, catalytic activity, periodate activation, oxidation.

Cite as

Sukhatskiy Yu. V., Shepida М. V., and Znak Z. O. Sonochemical synthesis and catalytic activity of the composite of Cu₂O–clinoptilolite nanoparticle. Physicochemical Mechanics of Materials. 2025. 61(4), 105-111.

https://doi.org/10.15407/pcmm2025.04.105

Abstract

A two-stage synthesis of the “Cu₂O nanoparticles–clinoptilolite” composite was carried out, which involved ultrasonic cavitation-intensified ion exchange of cations in the clinoptilolite framework for Cu²⁺ ions from an aqueous solution of copper sulfate and reduction of Cu²⁺ ions to Cu₂O nanoparticles with hydrazine. It was found that, in addition to the clinoptilolite peaks, the diffractogram of the synthesized material contained other peaks, which were mutually consistent with the cuprite (Cu₂O) model with a cubic structure, and the average size of the Cu₂O crystallite, calculated from the reflection assigned to the (111) plane, was ~ 13 nm. It was found that pseudospherical Cu₂O nanoparticles were uniformly distributed over the surface of the clinoptilolite framework, and the weighted average size of Cu₂O nanoparticles was ~ 61 nm. “Cu₂O nanoparticles–clinoptilolite” composite was tested as a catalyst for the decomposition of potassium periodate during the degradation of the Acid red 14 dye in an ultrasonic cavitation field. At a catalyst content in the reaction medium of 4 g/l, a dye degradation degree of 96.9% was achieved within 30 min. The scavenging method identified singlet oxygen as the dominant reactive oxygen form, which played a key role in dye degradation.

References

1. T. Derbe, S. Temesgen, and M. Bitew, “A short review on synthesis, characterization, and applications of zeolites,” Mater. Sci. and Eng., 2021 (2021). Article number 6637898. https://doi.org/10.1155/2021/6637898
2. L. Velarde, M. S. Nabavi, E. Escalera, M.-L. Antti, and F. Akhtar, “Adsorption of heavy metals on natural zeolites: A review,” Chemosphere, 328 (2023). Article number 138508. https://doi.org/10.1016/j.chemosphere.2023.138508
3. S. Kraljević Pavelić, J. Simović Medica, D. Gumbarević, A. Filošević, N. Pržulj, and K. Pavelić, “Critical review on zeolite clinoptilolite safety and medical applications in vivo,” Front Pharmacol., 9 (2018). Article number 1350. https://doi.org/10.3389/fphar.2018.01350
4. Y. Li, and J. Yu, “Emerging applications of zeolites in catalysis, separation and host-guest assembly,” Nat. Rev. Mater., 6, 1156-1174 (2021). https://doi.org/10.1038/s41578-021-00347-3
5. R. Srivastava, “Synthesis and applications of ordered and disordered mesoporous zeolites: Present and future prospective,” Catal. Today, 309, 172-188 (2018). https://doi.org/10.1016/j.cattod.2017.08.017
6. V. J. Inglezakis, “The сoncept of “сapacity” in zeolite ion exchange systems,” J. Colloid Interface Sci., 281, 68-79 (2005). https://doi.org/10.1016/j.jcis.2004.08.082
7. C. G. S. Lima, N. M. Moreira, M. W. Paixão, and A. G. Corrêa, “Heterogenous green catalysis: Application of zeolites on multicomponent reactions,” Curr. Opin. Green Sustain. Chem., 15, 7-12 (2019). https://doi.org/10.1016/j.cogsc.2018.07.006
8. I. G. B. N. Makertihartha, N. J. Azhari, and G. T. M. Kadja, “A review on zeolite application for aromatic production from non-petroleum carbon-based resources,” J. Eng. Technol. Sci., 55, No. 2, 131-142 (2023). https://doi.org/10.5614/j.eng.technol.sci.2023.55.2.3
9. U. Y. Qazi, R. Javaid, A. Ikhlaq, A. H. Khoja, and F. Saleem, “A comprehensive review on zeolite chemistry for catalytic conversion of biomass/waste into green fuels,” Molecules., 27(23) (2022). Article number 8578. https://doi.org/10.3390/molecules27238578
10. H. Serati-Nouri, A. Jafari, L. Roshangar, M. Dadashpour, Y. Pilehvar-Soltanahmadi, and N. Zarghami, “Biomedical applications of zeolite-based materials: A review,” Mater. Sci. Eng. C., 116 (2020). Article number 111225. https://doi.org/10.1016/j.msec.2020.111225
11. H. Valpotić, D. Gračner, R. Turk, D. Đuričić, S. Vince, I. Folnožić, M. Lojkić, I. Žura Žaja, L. Bedrica, N. Maćešić, I. Getz, T. Dobranić, and M. Samardžija, “Zeolite clinoptilolite nanoporous feed additive for animals of veterinary importance: potentials and limitations,” Periodicum Biol., 119, No. 3, 159-172 (2017). https://doi.org/10.18054/pb.v119i3.5434
12. A. Nikolov, L. Dobreva, S. Danova, J. Miteva-Staleva, E. Krumova, V. Rashev, and N. Neli Vilhelmova-Ilieva, “Natural and modified zeolite clinoptilolite with antimicrobial properties: A review,” Acta Microbiologica Bulgarica, 39, Is. 2, 147-161 (2023). https://doi.org/10.59393/amb23390207
13. D. Nunes, L. Santos, P. Duarte, A. Pimentel, J. V. Pinto, P. Barquinha, P. A. Carvalho, E. Fortunato, and R. Martins, “Room temperature synthesis of Cu2O nanospheres: Optical properties and thermal behavior,” Microscopy and Microanalysis, 21, Is. 1, 108-119 (2015). https://doi.org/10.1017/S1431927614013348
14. M. Guzman, W. Tian, C. Walker, and J. E. Herrera, “Copper oxide nanoparticles doped with lanthanum, magnesium and manganese: optical and structural characterization,” R. Soc. Open Sci., 9, Is. 11 (2022). Article number 220485. https://doi.org/10.1098/rsos.220485
15. Y. Sukhatskiy, Z. Znak, M. Sozanskyi, M. Shepida, P. R. Gogate, and V. Tsymbaliuk, “Activated periodates and sodium percarbonate in advanced oxidation processes of organic pollutants in aqueous media: A review,” Chem. Chem. Technol. 18, No. 2, 119-130 (2024). https://doi.org/10.23939/chcht18.02.119
16. Y. Sukhatskiy, M. Shepida, M. Sozanskyi, Z. Znak, and P. R. Gogate, “Periodate-based advanced oxidation processes for wastewater treatment: A review,” Sep. and Purif. Technol., 304 (2023). Article number 122305. https://doi.org/10.1016/j.seppur.2022.122305
17. Y. Sukhatskiy, M. Sozanskyi, M. Shepida, Z. Znak, and P. R. Gogate, “Decolorization of an aqueous solution of methylene blue using a combination of ultrasound and peroxate process,” Sep. and Purif. Technol., 288 (2022). Article number 120651. https://doi.org/10.1016/j.seppur.2022.120651
18. N. Zhang, L. Sun, S. Xu, H. Wei, and T. Song, “Periodate activation via metals and metal-based complexes: Progress in degradation properties and mechanisms,” Water Sci. Technol., 90, Is. 5, 1681-1705 (2024). https://doi.org/10.2166/wst.2024.292
19. X. Zhang, M. Verbist, M. Kamali, Y. Xue, Y. Liu, P. Jin, M. E. V. Costa, L. Appels, D. Cabooter, and R. Dewil, “Activation of periodate with pinewood biochar-CuO composite for the removal of recalcitrant organic pollutants – Mechanisms and degradation products,” Chem. Eng. J., 465 (2023). Article number 142916. https://doi.org/10.1016/j.cej.2023.142916
20. S. Musmade, D. Hase, A. Waghmare, K. Kadam, J. Khedkar, A. Gadhave, K. Bhavsar, and V. Murade, “Synthesis of shape controlled Cu2O and Cu2O/TiO2-QD composite for degradation of Congo red dye under visible-light irradiation,” J. Water Environ. Nanotechnol., 8, Is. 4, 406-416 (2023).
21. H. Aloulou, H. Bouhamed, A. Ghorbel, R. B. Amar, and S. Khemakhem, “Elaboration and characterization of ceramic microfiltration membranes from natural zeolite: Application to the treatment of cuttlefish effluents,” Desalin. and Water Treat., 95, 9-17 (2017). https://doi.org/10.5004/dwt.2017.21348
22. M. M. Mohamed, F. I. Zidan, and M. Thabet, “Synthesis of ZSM-5 zeolite from rice husk ash: Characterization and implications for photocatalytic degradation catalysts,” Microporous Mesoporous Mater., 108, Is. 1-3, 193-203 (2008). https://doi.org/10.1016/j.micromeso.2007.03.043
23. E. A. Kamila, Z. Abidin, I. I. Arief, and T. Trivadila, “Synthesis, characterization, antibacterial activity, and potential water filter application of copper oxide/zeolite composite,” Makara J. Sci., 27, Is. 3, 186-193 (2023). https://doi.org/10.7454/mss.v27i3.1555
24. D. Asmat-Campos, G. M. de Oca-Vásquez, J. Rojas-Jaimes, D. Delfín-Narciso, L. Juárez-Cortijo, R. Nazario-Naveda, D. B. Menezes, R. Pereira, and M. S. de la Cruz, “Cu2O nanoparticles synthesized by green and chemical routes, and evaluation of their antibacterial and antifungal effect on functionalized textiles,” Biotechnol. Rep., 37, (2023). Article number e00785. https://doi.org/10.1016/j.btre.2023.e00785
25. S. Hynniewta, M. Lily, and A. K. Chandra, “Computational investigations on kinetics of reaction between t-butanol and OH radical and ozone formation potential,” J. Mol. Gr. Model. 108 (2021). Article number 108002. https://doi.org/10.1016/j.jmgm.2021.108002
26. O. Fónagy, E. Szabó-Bárdos, and O. Horváth, “1,4-Benzoquinone and 1,4-hydroquinone based determination of electron and superoxide radical formed in heterogeneous photocatalytic systems,” J. Photochem. Photobiol. A Chem., 407 (2021). Article number 113057. https://doi.org/10.1016/j.jphotochem.2020.113057
27. N. Miyoshi, M. Ueda, K. Fuke, Y. Tanimoto, M. Itoh, and G. Tomita, “Lifetime of singlet oxygen and quenching by NaN3 in mixed solvents,” Z. Naturforsch. B, 37, 649-652 (1982). https://doi.org/10.1515/znb-1982-0520
28. Y. Li, J. Wang, Z. Wei, W. Li, W. Duan, X. Feng, Q. Ma, Q. Zhang, H. Chen, and X. Wu, “Effective periodate activation by peculiar Cu2O nanocrystal for antibiotics degradation: The critical role of structure and underlying mechanism study,” Appl. Catal. B Environ, 341 (2024). Article number 123351. https://doi.org/10.1016/j.apcatb.2023.123351