Preparation, characterization, adsorption, and antibacterial assessments of silane-functionalized zeolites
DOI:
https://doi.org/10.20450/mjcce.2025.3103Keywords:
natural zeolite, beta zeolite, nsilane-modified zeolite, , APTES, silver ion, antibacterial activityAbstract
In this study, the preparation and comparative analysis of two adsorbents based on silane-modified natural and synthetic zeolites for binding silver ions from aqueous solutions and evaluating their potential application as antibacterial agents against two strains of bacteria were conducted. (3-aminopropyl)triethoxysilane (APTES) was used for modification, and its presence in the resulting samples was confirmed by thermal analysis, BET surface area measurements, and infrared spectroscopy. Kinetic analysis showed that the silver adsorption process followed the Lagergren pseudo-second-order model, while the data were best described by the Freundlich isotherm, indicating multilayer adsorption on a heterogeneous surface. The maximum adsorption capacities for silver ions were 89.49 mg/g for natural zeolite and 61.19 mg/g for synthetic Beta zeolite. Natural zeolite exhibited a higher silver-binding capacity, leading to the conclusion that exchangeable cations in the structure of the starting material played a key role in silver binding and that ion exchange was the dominant mechanism. Both materials demonstrated good antibacterial properties against gram-negative Escherichia coli and the gram-positive Staphylococcus aureus. These findings highlighted the potential of APTES-modified zeolites as efficient adsorbents for silver ion removal and as antibacterial agents, paving the way for applications in water purification and antimicrobial technologies.
References
(1) Luan, H.; Xu, C.; Wu, Q.; Xiao, F. S., Recent advanc-es in the synthesis of TS-1 zeolite, Sec. Catalytic Re-actions and Chemistry 2022, 10.
https://doi.org/10.3389%2Ffchem.2022.1080554
(2) Ugrina, M.; Gaberšek, M.; Daković, A.; Nuić, I., Prep-aration and characterization of the sulfur-impregnated natural zeolite clinoptilolite for Hg(II) removal from aqueous solutions, Processes 2021, 9 (2), 217.
https://doi.org/10.3390/pr9020217
(3) Rajić, N.; Stojaković, Dj.; Jevtić, S.; Zabukovec Logar, N.; Kovač, J.; Kaučić, V., Removal of aqueous man-ganese using the natural zeolitic tuff from the Vranjska Banja deposit in Serbia, Journal of Hazard-ous Materials 2009, 172 (2–3), 1450–1457.
https://doi.org/10.1016/j.jhazmat.2009.08.011
(4) Rakić-Milojević, M.; Bogdanović-Bajuk, D., Recent advances in zeolites and porous materials applications in catalysis and adsorption processes, Catalysts 2023, 13 (5), 863. https://doi.org/10.3390/catal13050863
(5) Jevtić, S.; Arčon, I.; Rečnik, A.; Babić, B.; Mazaj, M.; Pavlović, J.; Matijašević, D.; Nikšić, M.; Rajić, N., The iron(III)-modified natural zeolitic tuff as an adsorbent and carrier for selenium oxyanions, Microporous and Mesoporous Materials 2014, 197, 92–100.
https://doi.org/10.1016/j.micromeso.2014.06.008
(6) Weckhuysen, B. M.; Yu, J., Recent advances in zeolite chemistry and catalysis, Chemical Society Reviews, 2015, Issue 20.
https://doi.org/10.1039/C5CS90100F
(7) Santos da Silva, A.; Novais da Rocha, Z.; Mignoni, M. L., Z. dos Santos, J. H., Solvent-free synthesis of mod-ified zeolites using hybrid silicas as raw material, Mi-croporous and Mesoporous Materials 2019, 290, 109684. https://doi.org/10.1016/j.micromeso.2019.109684
(8) Brazovskaya, E. Yu.; Golubeva, O. Yu., Study of the effect of isomorphic substitutions in the framework of zeolites with a beta structure on their porosity and sorption characteristics, Glass Physics and Chemistry 2017, 43, 357–362.
https://doi.org/10.1134/S1087659617040046
(9) Pasti, L.; Sarti, E.; Cavazzini, A.; Marchetti, N.; Dondi, F.; Martucci, A., Factors affecting drug adsorption on beta zeolite, Journal of Separation Science 2013, 36, (9–10) 1604-161. https://doi.org/10.1002/jssc.201201142
(10) Kuldeyev, Е.; Seitzhanova, М.; Sandugash Tanirber-genova, S.; Tazhu, K.; Doszhanov, E.; Mansurov, Z.; Azat, S.; Nurlybaev, R.; Berndtsson, R.; Modifying natural zeolites to improve heavy metal adsorption, Water 2023, 15 (12), 2215. https://doi.org/10.3390/w15122215
(11) Souza, I. M. S. Borrego-Sánchez, A.; Rigoti, E.; Sainz-Díaz, C. I.; Viseras, C.; Pergher, S. B. C., Experimental and molecular modelling study of beta zeolite as drug delivery system, Microporous and Mesoporous Mate-rials 2021, 321, 111152.
https://doi.org/10.1016/j.micromeso.2021.111152
(12) Miao, C.; Wang, L.; Zhou, S.; Yu, D.; Zhang, C.; Gao, S.; Yu, X.; Zhao, Z., Preparation of mesoporous zeo-lites and their applications in catalytic elimination of atmospheric pollutants, Catalysts 2024, 14 (1), 75.
https://doi.org/10.3390/catal14010075
(13) Shirendev, N.; Bat-Amgalan, M.; Kano, N.; Kim, H. J.; Gunchin, B.; Ganbat, B.; Yunden, G., A natural zeolite developed with 3-aminopropyltriethoxysilane and ad-sorption of Cu(II) from aqueous media, Appleid Sci-ence 2022, 12 (22), 11344.
https://doi.org/10.3390/app122211344
(14) Buffet-Bataillon, S.; Tattevin, P.; Bonnaure-Mallet, M.; Jolivet-Gougeon, A., Emergence of resistance to anti-bacterial agents: the role of quaternary ammonium compounds – a critical review, Int. J. Antimicrob. Agents 2012, 39 381–389.
http://dx.doi.org/10.1016/j.ijantimicag.2012.01.011
(15) Senila, M.; Cadar,O.; Modification of natural zeolites and their applications for heavy metal removal from polluted environments: Challenges, recent advances, and perspectives, Heliony 2024, 10 (3), e25303.
https://doi.org/10.1016/j.heliyon.2024.e25303
(16) Han, X.; Yu, J.; Cao, Z.; Wang, R.; Du, W.; He, P.; Ge, Y., Preparation and properties of silane coupling agent modified zeolite as warm mix additive, Con-struction and Building Materials 2020, 244, 118408.
https://doi.org/10.1016/j.conbuildmat.2020.118408
(17) Popaliya, M.; Mishra, A., Modified zeolite as an ad-sorbent for dyes, drugs, and heavy metal removal: a review, International Journal of Environmental Sci-ence and Technology 2023, 20, 12919–12936.
http://dx.doi.org/10.1007/s13762-022-04603-z
(18) Madden, D., Curtin, T., Carbon dioxide capture with amino-functionalised zeolite-b: A temperature pro-grammed desorption study under dry and humid con-ditions, Microporous and Mesoporous Materials 2016, 228, 310–317.
https://doi.org/10.1016/j.micromeso.2016.03.041
(19) Zhu, Z., Xu, H., Jiang, J., Wu, H., Wu, P., Hydropho-bic nanosized all-silica beta zeolite: efficient synthesis and adsorption application, ACS Appl. Mater. Inter-faces 2017, 9 (32), 27273–27283.
https://doi.org/10.1021/acsami.7b06173
(20) Pasti, L.; Sarti, E.; Cavazzini, A.; Marchetti, N.; Dondi, F.; Martucci, A., Factors affecting drug adsorption on beta zeolites, Separation science 2013, 36 (9–10), 1604-1611. https://doi.org/10.1002/jssc.201201142
(21) Saint-Cricq, P.; Kamimura, Y.; Itabashi, K.; Sugawara-Narutaki, A.; Shimojima, A.; Okubo, T., Antibacterial activity of silver-loaded "green zeolite", European Journal of Inorganic Chemistry 2012, 21, 3398–3402. https://doi.org/10.1002/ejic.201200476
(22) Dallas, P.; Sharma, V. K.; Zboril, R., Silver polymeric nanocomposites as advanced antimicrobial agents: classification, synthetic paths, applications, and per-spectives, Adv. Colloid Interface Sci. 2011, 166, 119–135. http://dx.doi.org/10.1016/j.cis.2011.05.008
(23) Han, X.; Zhilong Cao a; Wang, R.; He, P.; Zhang, Y.; Yu, J.; Ge, Y., Effect of silane coupling agent modi-fied zeolite warm mix additives on properties of as-phalt, Construction and Building Materials 2020, 259, 119713. https://doi.org/10.1016/j.conbuildmat.2020.119713
(24) Jelić, A.; Sekulić, M.; Travica, M.; Gržetić, J.; Ugri-nović, V.; Marinković, A. D.; Božić, A.; Stamenović, M.; Putić, S., Determination of mechanical properties of epoxy composite materials reinforced with silicate nanofillers using digital image correlation (DIC), Pol-ymers 2022, 14 (6), 1255.
https://doi.org/10.3390/polym14061255
(25) Özel, C.; Akat, C.; R. Alosmanov, A.; Kahveci, M. U.; Emir, C.; Yücel, S.; Surface modification of zeolite and kaolin with 3-(aminopropyl) triethoxysilane and 3-(trimethoxysilyl) propyl methacrylate. Bulgarian Chemical Communications 2021, 53 (4), 464–470.
DOI: 10.34049/bcc.53.4.T003464
(26) Veličković, Z. S.; Vuković, G. D.; Marinković, A. D.; Moldovan, M. S.; Perić-Grujić, A. A.; Uskoković, P. S.; Ristić, M. D., Adsorption of arsenate on iron(III) oxide coated ethylenediamine functionalized multiwall carbon nanotubes, Chem. Eng. J. 2012, 181–182, 174–181. https://doi.org/10.1016/j.cej.2011.11.052
(27) Miloševića, D. L.; Tomić, N. Z., Đokić, V. R.; Vidov-ića, M. M.; Veličković, Z. S., Jančić-Heinemann, R., Marinković, A. D., Structural and surface modification of highly ordered alumina for enhanced removal of Pb2+, Cd2+ and Ni2+ from aqueous solution, Desalina-tion and Water Treatment 2020, 178, 220–239.
https://doi.org/10.5004/dwt.2020.24982
(28) Hudzicki, J., Kirby-Bauer Disk Diffusion Susceptibil-ity. Test Protocol, 2009. Corpus ID: 125831583
(29) Dong, Y.; Lin, H.; He, Y., Correlation between physi-cochemical properties of modified clinoptilolite and its performance in the removal of ammonia-nitrogen, En-vironmental Monitoring and Assessment 2017, 189, 107. https://doi.org/10.1007/s10661-017-5806-9
(30) Ortegon, D.; Rojas, J.; Meza, J.; Diaz, E.; Roa, M.; Characterization of the clinoptilolite zeolite and its po-tential application as the basis of a filtering system for the oil industry, Journal of Physics: Conference Series 2021, 2046, 012044.
DOI:10.1088/1742-6596/2046/1/012044
(31) Collection of Simulated XRD Powder Patterns for Zeo-lites, Editors: M. M. J. Treacy and J. B. Higgins. Else-vier 2001. ISBN: 9780080529349
(32) Sher, A., Characterization of beta zeolites by X-ray diffraction, scanning electron microscope, and refrac-tive index techniques, Journal of the Chemical Society of Pakistan 2010, 32 (5), 592–598.
(33) Kukobat, R.; Škrbić, R.; Massiani, P.; Baghdad, K.; Launay, F.; Sarno, M.; Cirillo, C.; Senadore, A.; Salcin, E.; Atlagić, S. G., Thermal and structural stabil-ity of microporous natural clinoptilolite zeolite, Mi-croporous and Mesoporous Materials 2022, 341, 112101.
https://doi.org/10.1016/j.micromeso.2022.112101
(34) Mitchell, S.; Bonilla, A.; Pérez-Ramírez, J., Preparation of organic-functionalized mesoporous ZSM-5 zeolites by consecutive desilication and silanization, Materials Chemistry and Physics 2011, 127 (1–2), 278–284. https://doi.org/10.1016/j.matchemphys.2011.02.003
(35) Zendelska, A.; Golomeova, M.; Jakupi, Š.; Ku-vendziev, S.; Lisichkov, K.; Marinkovski, M., Charac-terization and application of clinoptilolite for removal of heavy metal ions from water resources, Geologica Macedonica 2018, 32 (1), 21–32.
(36) Akata, B.; Yilmaz, B.; Jirapongphan, S. S.; Warzywoda, J.; Sacco Jr, A., Characterization of zeo-lite Beta grown in microgravity, Microporous and Mesoporous Materials 2004, 71 (1–3), 1–9.
https://doi.org/10.1016/j.micromeso.2004.03.012
(37) Chen, T.; Gu, C.; Ouyang, Y.; Zhuang, L.; Yao, Z.; Zou, K.; Wang, Y.; Luo, Y.; Shu, X., Synthesis of high hydrothermal stability Beta zeolite with crosslinked starch and catalytic performance in catalytic cracking reaction, Fuel 2022, 318, 123696.
https://doi.org/10.1016/j.fuel.2022.123696
(38) Bayat, M.; Javanbakht, V.; Esmai, J., Synthesis of zeolite/nickel ferrite/sodium alginate bionanocompo-site via a co-precipitation technique for efficient re-moval of water-soluble methylene blue dye, Interna-tional Journal of Biological Macromolecules 2018, 116, 607–619.
https://doi.org/10.1016/j.ijbiomac.2018.05.012
(39) Moradmard, H.; Shayesteh, S. F.; Tohidi, P.; Abbas, Z.; Khaleghi, M., Structural, magnetic and dielectric properties of magnesium doped nickel ferrite nanopar-ticles, Journal of Alloys and Compounds 2015, 650, 116–122.
(40) Daemi, H.; Barikani, M.; Barmar, M., Variations in calcium and alginate ions concentration in relation to the properties of calcium alginate nanoparticles, Sci-ence and Technology 2013, 26 (1), 25–32.
(41) Holub, M., Balintova, M., Demcak, S., Hurakova, M., Characterization of natural zeolite and determination its adsorption properties, Journal of Civil Engineering, Environment and Architecturs, 2016.
DOI:10.7862/rb.2016.192
(42) Breck, D. W., Zeolite molecular sieves: structure, chemistry, and use. Wiley-Interscience Journal of Chromatographic Science 1975, 13 (4), 18A.
https://doi.org/10.1093/chromsci/13.4.18A-c
(43) Mintova, S.; Gilson, J. P.; Valtchev, V., Advances in the nanoscale engineering of zeolites for applications in catalysis and adsorption. Chemical Society Reviews 2013, 42 (9), 3690–3707.
https://doi.org/10.1039/C3CS35457C
(44) Cundy, C. S.; Cox, P. A., The hydrothermal synthesis of zeolites: history and development from the earliest days to the present time. Chemical Reviews 2003, 103 (3), 663–701. https://doi.org/10.1021/cr020060i
(45) Jevtić, S., Dimitrijević, J., Petrović, J., Dikić, J., Anti-bacterial activity of surface amine-functionalized sil-ver-enriched zeolite , XIV Conference of chemists, technologists and environmentalists of Republic of Srpska, 2022, 178–178 Banja Luka: University in Banja Luka, Faculty of Technology.
(46) Petrović, J.; Stojanović, M.; Milojković, J.; Petrović, M.; Šoštarić, T.; Laušević, M.; Mihajlović, L. M., Al-kali modified hydrochar of grape pomace as a per-spective adsorbent of Pb2+ from aqueous solution, Journal of Environmental Management 2016, 182, 292–300.
https://doi.org/10.1016/j.jenvman.2016.07.08119
(47) Dimitrijević, J.; Jevtić, S.; Marinković, A.; Simić, M.; Koprivica, M.; Petrović, J., Ability of deep eutectic solvent modified oat straw for Cu(II), Zn(II), and Se(IV) ions removal. Processes 2023, 11.
https://doi.org/10.3390/pr11051308
(48) Abdellaoui, Y.; El Ibrahimi, B.; Ahrouch, M.; Zineb Kassab, Z.; Billah, R. E. K.; Coppel, Y.; López-Maldonado, E. A.; Oualid, A. O.; Díaz de León, J. N.; Leiviskä, T.; Giácoman-Vallejos, G.; Gamero-Melo, P., New hybrid adsorbent based on APTES functional-ized zeolite W for lead and cadmium ions removal: Experimental and theoretical studies, Chemical Engi-neering Journal 2024, 499, 156056.
https://doi.org/10.1016/j.cej.2024.156056
(49) Velarde, L.; Nabavi, S. M.; Escalera, E.; Antti, L. M.; Akhtar, F., Adsorption of heavy metals on natural zeo-lites: A review, Chemosphere 2023, 328, 138508. https://doi.org/10.1016/j.chemosphere.2023.138508
(50) Lagergren, S., Zur Theorie der sogenannten Adsorp-tion gelöster Stoffe, K. Sven. Vetenskapsakad. Handl. 1898; 24, pp. 1–39. https://doi.org/10.1007/BF01501332
(51) Ho, Y. S.; McKay, G., Pseudo-second order model for sorption processes, Process Biochem. 1999, 34, 451–465. https://doi.org/10.1016/S0032-9592(98)00112-5
(52) Weber, W.; Morris, J., Kinetics of adsorption on car-bon from solution, J. Sanit. Eng. Div. 1963, 89, 31–60. https://doi.org/10.1061/JSEDAI.0000430
(53) Simić, M.; Petrović, J.; Šoštarić, T.; Ercegović, M.; Milojković, J.; Lopičić, Z.; Kojić, M., A mechanism assessment and differences of cadmium adsorption on raw and alkali-modified agricultural waste, Processes 2022, 10 (10), 1957. https://doi.org/10.3390/pr10101957
(54) Petrović, J.; Ercegović, M.; Simić, M.; Kalderis, D.; Koprivica, M.; Milojović, J.; Radulović, D.; Novel Mg-doped pyro-hydrochars as methylene blue adsorbents: Adsorption behavior and mechanism, Journal of Mo-lecular Liquids 2023, 376, 121424.
https://doi.org/10.1016/j.molliq.2023.121424
(55) Langmuir, I., The adsorption of gases on plane surfac-es of glass, mica and platinum, J. Am. Chem. Soc. 1918, 40, 1361–1403. https://doi.org/10.1021/ja02242a004
(56) Webber, T. W.; Chakkravorti, R. K., Pore and solid diffusion models for fixed-bed adsorbers, AlChE J. 1974, 20, 228–238.
https://doi.org/10.1002/aic.690200204
(57) Foo, K. Y.; Hameed, B. H., Insights into the modeling of adsorption isotherm systems, Chem. Eng. J. 2010, 156, 2–10. https://doi.org/10.1016/j.cej.2009.09.013
(58) Freundlich, H. M. F., Über die Adsorption in Lösung-en, Z. Phys. Chem. 1906, 57 A, 385–470.
https://doi.org/10.1515/zpch-1907-5723
(59) Temkin, M. I., and Pyzhev, V., Kinetic of ammonia synthesis on promoted iron catalyst, Acta Phy. Chem, URSS 12, 327-356, 1940.
(60) Slavin, Y. N.; Asnis, J.; Häfeli, U. O.; Bach, H., Metal nanoparticles: understanding the mechanisms behind antibacterial activity, Journal of Nanobiotechnology 2017, 15, 65. https://doi.org/10.1186/s12951-017-0308-z
Downloads
Published
Versions
- 2025-12-24 (2)
- 2025-12-04 (1)
How to Cite
Issue
Section
License
Copyright (c) 2025 Jelena Dimitrijević, Jelena Petrović, Aleksandar Marinković, Jelena Dikić, Marija Koprivica, Marija Simić, Sanja Jevtić
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
