Сорбційне вилучення катіонів цезію гібридним матеріалом на основі ZIF-8 та фероціаніду міді з водного середовища

N.V. Roik; M.V. Ischenko; О.S. Roik; L.F. Sharanda; І.М. Trofymchuk; P.P. Gorbyk

doi:10.15407/hftp17.02.225

Authors

N.V. Roik Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine https://orcid.org/0000-0001-6286-8583
M.V. Ischenko Taras Shevchenko National University of Kyiv https://orcid.org/0000-0002-0851-1679
О.S. Roik Taras Shevchenko National University of Kyiv https://orcid.org/0000-0001-9705-1100
L.F. Sharanda Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine https://orcid.org/0009-0009-3698-7568
І.М. Trofymchuk Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine https://orcid.org/0000-0002-0955-1103
P.P. Gorbyk Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine https://orcid.org/0000-0002-4954-336X

DOI:

https://doi.org/10.15407/hftp17.02.225

Keywords:

caesium cations, zeolitic imidazolate frameworks, copper hexacyanoferrate, selective sorption, sorption parameters

Abstract

Concentration and removal of heavy metal ions and radioactive isotopes from multicomponent aqueous solutions remain an urgent task today due to the danger of anthropogenic pollution of the environment. The aim of the work was to create an effective sorbent based on an organometallic zeolitic imidazolate carrier and copper hexacyanoferrate possessing high kinetic and sorption parameters as well as selectivity towards cesium cations. The synthesis of the Zn-containing zeolitic imidazolate structure ZIF-8, subsequent partial substitution of Zn²⁺ by Cu²⁺, and formation of hexacyanoferrate crystal lattice were carried out in an aqueous medium at room temperature. The crystalline and porous structure of synthesized materials was investigated using X-ray diffraction analysis and low-temperature nitrogen adsorption-desorption, respectively. Obtained results confirm formation of ZIF-8 material with typical sodalite topology, high specific surface area, large total pore volume, and homogeneous microporous structure. It was proven that the interaction of the synthesized ZIF-8 with copper nitrate and subsequent modification with potassium hexacyanoferrate(II) leads to the formation of face-centered cubic crystalline structure.

The study of sorption efficiency of synthesized hybrid material towards cesium cations was carried out in static mode depending on the acidity of medium, duration of contact, equilibrium concentration of adsorbate and presence of other cations in aqueous solution. It was found that the value of cesium cations sorption remains constant in the pH range from 6 to 9. The experimentally obtained results of equilibrium sorption studies were analyzed using kinetic (Lagergren and Ho-McKay) and isothermal (Langmuir and Freundlich) models. It was found that cesium cations sorption is described by pseudo-second-order kinetic model, according to which the interaction of adsorbate with surface centers of hybrid sorbent occurs quite quickly and diffusion is the main limiting factor of this process. It was proven that the equilibrium sorption of cesium cations is consistent with the Freundlich model, which describes the interaction of adsorbate with energetically nonequivalent surface sites of adsorbent. It was found that hybrid organometallic-coordinational material is capable of Cs⁺ selective removal from aqueous solutions containing excess amounts of Na⁺, K⁺ or Ca²⁺. The obtained results may be useful in the creation of new sorption materials for water purification from Cs⁺.

References

1. Lee S., Kim M., Lee J. Analyzing the impact of nuclear power on CO2 emissions. Sustain. 2017. 9(8): 1428. https://doi.org/10.3390/su9081428

2. Soto G.H., Martinez-Cobas X. Nuclear energy generation's impact on the CO2 emissions and ecological footprint among European Union countries. Sci. Total Environ. 2024. 945: 173844. https://doi.org/10.1016/j.scitotenv.2024.173844

3. Radionuclides in the environment. Ed. by Atwood D.A. (Chichester: Wiley, 2010).

4. Kivan O., Yusuf M., Filson-Halliwell R., Enemmoh J.N., Harbottle D., Hunter T.N. Intensified co-precipitation and ion exchange using an agitated tubular reactor (ATR) for enhanced removal of Cs+ and Sr2+ ions. Chem. Engin. Proc. - Proc. Int. 2025. 207: 110077. https://doi.org/10.1016/j.cep.2024.110077

5. Bengiat R., Bogoslavsky B., Mandler D., Almog J. Selective binding and precipitation of cesium ions from aqueous solutions: a size-driven supramolecular reaction. Chem. ? A Eur. J. 2018. 24(13): 3161. https://doi.org/10.1002/chem.201706181

6. Lee H.K., Jun B.M., Kim S.I., Song J.S., Kim T.J., Park S., Chang S. Simultaneous removal of suspended fine soil particles, strontium and cesium from soil washing effluent using inorganic flocculants. Environ. Technol. Innov. 2022. 27: 102467. https://doi.org/10.1016/j.eti.2022.102467

7. Luo H., Huang J.F., Dai S. Solvent extraction of Sr2+ and Cs+ using protic amide-based ionic liquids. Sep. Sci. Technol. 2010. 45(12-13): 1679. https://doi.org/10.1080/01496395.2010.493798

8. Li W.-A., Peng Y.-C., Ma W., Huang X.-Y., Feng M.-L. Rapid and selective removal of Cs+ and Sr2+ ions by two zeolite-type sulfides via ion exchange method. Chem. Eng. J. 2022. 442(2): 136377. https://doi.org/10.1016/j.cej.2022.136377

9. Kwon S., Kim C., Han E., Lee H., Cho H.S., Choi M. Relationship between zeolite structure and capture capability for radioactive cesium and strontium. J. Hazard. Mater. 2021. 408: 124419. https://doi.org/10.1016/j.jhazmat.2020.124419

10. Wang K., Ma H., Pu S., Yan C., Wang M., Yu J., Wang X., Chu W., Zinchenko A. Hybrid porous magnetic bentonite-chitosan beads for selective removal of radioactive cesium in water. J. Hazard. Mater. 2019. 362: 160. https://doi.org/10.1016/j.jhazmat.2018.08.067

11. Eom H.H., Kim Y., Harbottle D., Lee J.W. Immobilization of KTS-3 on an electrospun fiber membrane for efficient removal of Cs+ and Sr2+. J. Environ. Chem. Eng. 2021. 9(5): 105991. https://doi.org/10.1016/j.jece.2021.105991

12. Zhang H., Li C., Chen X., Fu H., Chen Y., Ning S., Fujita T., Wei Y., Wang X. Layered ammonium vanadate nanobelt as efficient adsorbents for removal of Sr2+ and Cs+ from contaminated water. J. Colloid Interface Sci. 2022. 615: 110. https://doi.org/10.1016/j.jcis.2022.01.164

13. Khandaker S., Kuba T., Kamida S., Uchikawa Y. Adsorption of cesium from aqueous solution by raw and concentrated nitric acid-modified bamboo charcoal. J. Environ. Chem. Eng. 2017. 5(2): 1456. https://doi.org/10.1016/j.jece.2017.02.014

14. Yang H.M., Kim S.W., Kim H.J., Lee G.E., Jang J.Y. Surface decontamination of radioactive cesium by a reversibly cross-linkable hydrogel using poly(vinyl alcohol) and phenylboronic acid-grafted poly(methyl vinyl ether-alt-mono-sodium maleate). Chemosphere. 2023. 339: 139617. https://doi.org/10.1016/j.chemosphere.2023.139617

15. Kim Y.K., Kim S., Kim Y., Bae K., Harbottle D., Lee J.W. Facile one-pot synthesis of dual-cation incorporated titanosilicate and its deposition to membrane surfaces for simultaneous removal of Cs+ and Sr2+. Appl. Surf. Sci. 2019. 493: 165. https://doi.org/10.1016/j.apsusc.2019.07.008

16. Dong C., Deng X., Guo X., Wang B., Ye X., Fan J., Zhu C., Fan F., Qing B. Synthesis of potassium metal ferrocyanide/Al-MCM-41 with fast and selective adsorption of cesium. Colloids Surf. A. 2021. 613: 126107. https://doi.org/10.1016/j.colsurfa.2020.126107

17. Kim M., Eun S., Ryu J., Kim S. Efficient removal of Cs ion by electrochemical adsorption and desorption reaction using NiFe Prussian blue deposited carbon nanofiber electrode. J. Hazard. Mater. 2023. 443: 130215. https://doi.org/10.1016/j.jhazmat.2022.130215

18. Wang Y., Li F., Mao J., Wang X., Shao Y., Yuan J. Magnetic copper hexacyanoferrate core-shell nanoparticles for effective cesium removal from aqueous solutions. Environ. Sci.: Water Res. Technol. 2023. 9(4): 1115. https://doi.org/10.1039/D2EW00712F

19. Su M., Chen M., Liu H., Han W., Chen D., Xu J., Tang J. Highly efficient removal of Cs(I) using the magnetically separable potassium ferrocyanide: Mechanism, economic analysis, and impact insights. J. Cleaner Prod. 2023. 423: 138734. https://doi.org/10.1016/j.jclepro.2023.138734

20. Yang H.-M., Hwang K.S., Park C.W., Lee K.-W. Sodium-copper hexacyanoferrate-functionalized magnetic nanoclusters for the highly efficient magnetic removal of radioactive caesium from seawater. Water Res. 2017. 125: 81. https://doi.org/10.1016/j.watres.2017.08.037

21. Guzii S., Arkhypenko O., Odukalets L., Prysiazhna O., Rashkevich N. Magnetite-ferrocyanide-copper sorbents for recovery of cesium ions from low-activity liquid radioactive waters. Mater. Sci. Eng. 2024. 8(1): 15. https://doi.org/10.15406/mseij.2024.08.00230

22. Thierry V., Vincent C., Barre Y., Guari Y., Le Saout G., Guibal E. Immobilization of metal hexacyanoferrates in chitin beads for cesium sorption: synthesis and characterization. J. Mater. Chem. A. 2014. 2(26): 10007. https://doi.org/10.1039/c4ta01128g

23. Okamura Y., Fujiwara K., Ishihara R., Sugo T., Kojima T., Umeno D., Saito K. Cesium removal in freshwater using potassium cobalt hexacyanoferrate-impregnated fibers. Radiat. Phys. Chem. 2014. 94: 119. https://doi.org/10.1016/j.radphyschem.2013.04.011

24. Kim Y.K., Kim Y., Kim S., Harbottle D., Lee J.W. Solvent-assisted synthesis of potassium copper hexacyanoferrate embedded 3D-interconnected porous hydrogel for highly selective and rapid cesium ion removal. J. Environ. Chem. Eng. 2017. 5(1): 975. https://doi.org/10.1016/j.jece.2017.01.026

25. Pouramini Z., Mousavi S.M., Babapoor A., Hashemi S.A., Lai C.W., Mazaheri Y., Chiang W.-H. Effect of metal atom in zeolitic imidazolate frameworks (ZIF-8 & 67) for removal of dyes and antibiotics from wastewater: a review. Catalysts. 2023. 13(1): 155. https://doi.org/10.3390/catal13010155

26. Mo Z., Tai D.Z., Zhang H., Shahab A. A comprehensive review on the adsorption of heavy metals by zeolite imidazole framework (ZIF-8) based nanocomposite in water. Chem. Eng. J. 2022. 443: 136320. https://doi.org/10.1016/j.cej.2022.136320

27. Miensah E.D., Khan M.M., Chen J.Y., Zhang X.M., Wang P., Zhang Z.X., Yang Y. Zeolitic imidazolate frameworks and their derived materials for sequestration of radionuclides in the environment: a review. Critical Rev. Environ. Sci. Technol. 2019. 50(18): 1874. https://doi.org/10.1080/10643389.2019.1686946

28. Lu X., Liu Z., Wang X., Liu Y., Ma H., Cao M., Wang W., Yan T. Construction of MnO2@ZIF-8 core-shell nanocomposites for efficient removal of Sr2+ from aqueous solution. Colloids Surf. A. 2024. 685: 133317. https://doi.org/10.1016/j.colsurfa.2024.133317

29. Le Q.T.N., Cho K. Caesium adsorption on a zeolitic imidazolate framework (ZIF-8) functionalized by ferrocyanide. J. Colloid Int. Sci. 2021. 581: 741. https://doi.org/10.1016/j.jcis.2020.08.017

30. Zhang C., Lively R.P., Zhang K., Johnson J.R., Karvan O., Koros W.J. Unexpected molecular sieving properties of zeolitic imidazolate framework-8. J. Phys. Chem. Lett. 2012. 3(16): 2130. https://doi.org/10.1021/jz300855a

31. Rietveld H.M. A profile refinement method for nuclear and magnetic structures. J. Appl. Crystallogr. 1969. 2: 65. https://doi.org/10.1107/S0021889869006558

32. Takahashi A., Tanaka H., Minami K., Noda K., Ishizaki M., Kurihara M., Ogawa H., Kawamoto T. Unveiling Cs-adsorption mechanism of Prussian blue analogs: Cs+-percolation via vacancies to complete dehydrated state. RSC Adv. 2018. 8(61): 34808. https://doi.org/10.1039/C8RA06377J

33. Burgess J. Metal ions in solution. (Chichester: Ellis Horwood Limited, 1978).

34. Barrett E.P., Joyner L.G., Halenda P.H. The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J. Am. Chem. Soc. 1951. 73(1): 373. https://doi.org/10.1021/ja01145a126

35. Neimark A.V., Ravikovitch P.I., Grun M., Schuth F., Unger K.K. Pore size analysis of MCM-41 type adsorbents by means of nitrogen and argon adsorption. J. Colloid. Int. Sci. 1998. 207(1): 159. https://doi.org/10.1006/jcis.1998.5748

36. Gregg S.H., Sing K.S. Adsorption, surface area and porosity. (New York: Academic Press, 1967). https://doi.org/10.1149/1.2426447

37. Andersson J., Stroem A., Svemar C., Almen K.-E., Ericsson L.O. What requirements does the KBS-3 repository make on the host rock? Geoscientific suitability indicators and criteria for siting and site evaluation. (Stockholm: SKB, 2000).

38. Kim Y.K., Kim T., Kim Y., Harbottle D., Lee J.W. Highly effective Cs+ removal by turbidity-free potassium copper hexacyanoferrate-immobilized magnetic hydrogels. J. Hazard. Mater. 2017. 340: 130. https://doi.org/10.1016/j.jhazmat.2017.06.066

39. Vincent T., Vincent C., Guibal E. Immobilization of metal hexacyanoferrate ion-exchangers for the synthesis of metal ion sorbents ? A mini-review. Molecules. 2015. 20(11): 20582. https://doi.org/10.3390/molecules201119718

40. Wu C., Xiong Z., Li C., Zhang J. Zeolitic imidazolate metal organic framework ZIF-8 with ultra-high adsorption capacity bound tetracycline in aqueous solution. RSC Adv. 2015. 5(100): 82127. https://doi.org/10.1039/C5RA15497A

41. Ding Y., Xu Y., Ding B., Li Z., Xie F., Zhang F., Wang H., Liu J., Wang X. Structure induced selective adsorption performance of ZIF-8 nanocrystals in water. Colloids Surf. A. 2017. 520: 661. https://doi.org/10.1016/j.colsurfa.2017.02.012

42. Trung N.D., Ping N., Dan H.K. Application of mesopores copper hexacyanoferrate (II) nanomaterials for cesium adsorption. Environ. Eng. Res. 2023. 28(6): 220389. https://doi.org/10.4491/eer.2022.389

43. Mimura H., Kimura M., Akiba K., Onodera Y. Selective removal of cesium from highly concentrated sodium nitrate neutral solutions by potassium nickel hexacyanoferrate(II)-loaded silica gels. Solvent Extr. Ion Exch. 1999. 17: 403. https://doi.org/10.1080/07366299908934620

44. Vincent T., Vincent C., Barre Y., Guari Y., Le Saout G., Guibal E. Immobilization of metal hexacyanoferrates in chitin beads for cesium sorption: Synthesis and characterization. J. Mater. Chem. A. 2014. 2(26): 10007. https://doi.org/10.1039/c4ta01128g

45. Thammawong C., Opaprakasit P., Tangboriboonrat P., Sreearunothai P. Prussian blue-coated magnetic nanoparticles for removal of cesium from contaminated environment. J. Nanopart. Res. 2013. 15: 1689. https://doi.org/10.1007/s11051-013-1689-z

46. Lyashenko D.Yu., Gorbyk P.P. Nanostructure aerosylogel modified with aminopropyl groups as an effective sorbent of strontium(II) ions. Theor. Exp. Chem. 2025. 61(1): 59. [in Ukrainian]. https://doi.org/10.1007/s11237-025-09854-8