Abstract
Removal of the β-blocker atenolol from an aqueous solution was studied using TiO2/zeolites, prepared by a simple and cost-effective solid-state dispersion method. Synthetic zeolites 13X and ZSM-5 (Si/Al = 40) and natural zeolite clinoptilolite were used as one component of the hybrid materials, whereas TiO2 nanocrystals obtained from TiO2 nanotubes and P25 TiO2 nanoparticles were used as the other. The synthesized materials were characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transformed infrared spectroscopy, ultraviolet–visible diffuse reflectance spectroscopy and scanning electron microscopy with energy-dispersive spectroscopy. The photocatalytic activity for the degradation of atenolol was investigated under simulated solar light. Additionally, the effect of initial pH on atenolol removal and the reusability of prepared catalysts were tested. The best loading of TiO2 was 20 wt% over all investigated zeolites. The degradation of atenolol followed the pseudo-first-order kinetics. The photocatalytic degradation of atenolol after 70 min of irradiation was ~ 50% for TiO2/13X materials, ~ 45% for clinoptilolite combined with P25 TiO2 and ~ 57% for clinoptilolite combined with TiO2 nanocrystals obtained from TiO2 nanotubes. The results showed the highest removal efficiency after 70 min of irradiation for ZSM-5 combined with P25 TiO2 (~ 94%), followed by ZSM-5 combined with TiO2 nanocrystals obtained from TiO2 nanotubes (~ 88%) at near-neutral pH (~ 6.5). The total removal of atenolol from an aqueous solution for TiO2/ZSM-5 materials resulted from two processes: adsorption and photocatalytic degradation. The TiO2/ZSM-5 photocatalysts can be easily recovered and reused as their activity was preserved after four cycles.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Ahmed SN, Haider W (2018) Heterogeneous photocatalysis and its potential applications in water and wastewater treatment: a review. Nanotechnology 29:342001. https://doi.org/10.1088/1361-6528/aac6ea
Alvarez-Aguiñaga EA, Elizalde-González MP, Sabinas-Hernández SA (2020) Unpredicted photocatalytic activity of clinoptilolite-mordenite natural zeolite. RSC Adv 10:39251–39260. https://doi.org/10.1039/d0ra06421a
Babić S, Horvat AJM, Mutavdžić Pavlović D, Kaštelan-Macan M (2007) Determination of pKa values of active pharmaceutical ingredients. Trends Anal Chem 26:1043–1061. https://doi.org/10.1016/j.trac.2007.09.004
Baerlocher C, Meier WM, Olson DH (2001) Atlas of zeolite framework types, 5th edn. Elsevier, Amsterdam
Bhatia V, Malekshoar G, Dhir A, Ray AK (2017) Enhanced photocatalytic degradation of atenolol using graphene TiO2 composite. J Photochem Photobiol A Chem 332:182–187. https://doi.org/10.1016/j.jphotochem.2016.08.029
Cerjan Stefanović Š, Zabukovec Logar N, Margeta K et al (2007) Structural investigation of Zn2+ sorption on clinoptilolite tuff from the Vranjska Banja deposit in Serbia. Microporous Mesoporous Mater 105:251–259. https://doi.org/10.1016/j.micromeso.2007.04.033
Chang CT, Wang JJ, Ouyang T et al (2015) Photocatalytic degradation of acetaminophen in aqueous solutions by TiO2/ZSM-5 zeolite with low energy irradiation. Mater Sci Eng B 196:53–60. https://doi.org/10.1016/j.mseb.2014.12.025
Chang PH, Jiang WT, Sarkar B et al (2019) The triple mechanisms of atenolol adsorption on Ca-montmorillonite: implication in pharmaceutical wastewater treatment. Mater 12:2858. https://doi.org/10.3390/ma12182858
Corma A, Garcia H (2004) Zeolite-based photocatalysts. Chem Commun. https://doi.org/10.1039/B400147H
DellaGreca M, Iesce MR, Pistillo P et al (2009) Unusual products of the aqueous chlorination of atenolol. Chemosphere 74:730–734. https://doi.org/10.1016/j.chemosphere.2008.09.067
Diban N, Pacuła A, Kumakiri I et al (2021) TiO2-zeolite metal composites for photocatalytic degradation of organic pollutants in water Catalysts 11:1367 https://doi.org/10.3390/catal11111367
Duan X, Yang J, Hu G et al (2021) Optimization of TiO2/ZSM-5 photocatalysts: energy band engineering by solid state diffusion method with calcination. J Environ Chem Eng 9:105563. https://doi.org/10.1016/j.jece.2021.105563
Esteves de Castro RAE, Canotilho J, Barbosa RM, Redinha JS (2007) Infrared spectroscopy of racemic and enantiomeric forms of atenolol. Spectrochim Acta Part A Mol Biomol Spectrosc 67:1194–1200. https://doi.org/10.1016/j.saa.2006.10.007
Flanigen EM, Khatami H, Szymanski HA (1974) Infrared structural studies of zeolite frameworks In: Flanigen EM, Sand LB (eds) Molecular Sieve Zeolites-I, American Chemical Society, Washington D.C., pp 201–229 https://doi.org/10.1021/ba-1971-0101.ch016
Fujishima A, Rao TN, Tryk DA (2000) Titanium dioxide photocatalysis. J Photochem Photobiol C Photochem Rev 1:1–21. https://doi.org/10.1016/S1389-5567(00)00002-2
Gomez S, Marchena CL, Pizzio L et al (2013) Preparation and characterization of TiO2/HZSM-11 zeolite for photodegradation of dichlorvos in aqueous solution. J Hazard Mater 258–259:19–26. https://doi.org/10.1016/j.jhazmat.2013.04.030
Gomez S, Marchena CL, Renzini MS et al (2015) In situ generated TiO2 over zeolitic supports as reusable photocatalysts for the degradation of dichlorvos. Appl Catal B Environ 162:167–173. https://doi.org/10.1016/j.apcatb.2014.06.047
Govindan K, Sumanasekara VDW, Jang A (2020) Mechanisms for degradation and transformation of β-blocker atenolol via electrocoagulation, electro-Fenton, and electro-Fenton-like processes. Environ Sci Water Res Technol 6:1465–1481. https://doi.org/10.1039/d0ew00114g
Guesh K, Márquez-álvarez C, Chebude Y, Díaz I (2016) Enhanced photocatalytic activity of supported TiO2 by selective surface modification of zeolite Y. Appl Surf Sci 378:473–478. https://doi.org/10.1016/j.apsusc.2016.04.029
Hapeshi E, Achilleos A, Vasquez MI et al (2010) Drugs degrading photocatalytically: kinetics and mechanisms of ofloxacin and atenolol removal on titania suspensions. Water Res 44:1737–1746. https://doi.org/10.1016/j.watres.2009.11.044
Hu Y, Fitzgerald NM, Lv G et al (2015) Adsorption of atenolol on kaolinite. Adv Mater Sci Eng 2015:897870. https://doi.org/10.1155/2015/897870
Hu G, Yang J, Duan X et al (2021) Recent developments and challenges in zeolite-based composite photocatalysts for environmental applications. Chem Eng J 417:129209. https://doi.org/10.1016/j.cej.2021.129209
Ioannou LA, Hapeshi E, Vasquez MI et al (2011) Solar/TiO2 photocatalytic decomposition of β-blockers atenolol and propranolol in water and wastewater. Sol Energy 85:1915–1926. https://doi.org/10.1016/j.solener.2011.04.031
Jansson I, Suárez S, Javier Garcia-Garcia F, Sánchez S (2015) Zeolite-TiO2 hybrid composites for pollutant degradation in gas phase. Appl Catal b: Environ 178:100–107. https://doi.org/10.1016/j.apcatb.2014.10.022
Ji Y, Zhou L, Ferronato C et al (2013) Photocatalytic degradation of atenolol in aqueous titanium dioxide suspensions: kinetics, intermediates and degradation pathways. J Photochem Photobiol A Chem 254:35–44. https://doi.org/10.1016/j.jphotochem.2013.01.003
Khodadoust S, Sheini A, Armand N (2012) Photocatalytic degradation of monoethanolamine in wastewater using nanosized TiO2 loaded on clinoptilolite. Spectrochim Acta Part A Mol Biomol Spectrosc 92:91–95. https://doi.org/10.1016/j.saa.2012.01.082
Kovács K, Tóth T, Wojnárovits L (2022) Evaluation of advanced oxidation processes for β-blockers degradation: a review. Water Sci Technol 85:685–705. https://doi.org/10.2166/wst.2021.631
Küster A, Alder AC, Escher BI et al (2010) Environmental risk assessment of human pharmaceuticals in the European Union: a case study with the β-blocker atenolol. Integr Environ Assess Manag 6:514–523. https://doi.org/10.1897/IEAM_2009-050.1
Li Z, Fitzgerald NM, Lv G et al (2015) Adsorption of atenolol on talc: an indication of drug interference with an excipient. Adsorpt Sci Technol 33:379–392. https://doi.org/10.1260/0263-6174.33.4.379
Liu X, Liu Y, Lu S et al (2018) Performance and mechanism into TiO2/zeolite composites for sulfadiazine adsorption and photodegradation. Chem Eng J 350:131–147. https://doi.org/10.1016/j.cej.2018.05.141
Mao Z, Xu B, Ji X et al (2015) Titanium dioxide nanoparticles alter cellular morphology via disturbing the microtubule dynamics. Nanoscale 7:8466–8475. https://doi.org/10.1039/c5nr01448d
Marques SCR, Mestre AS, Machuqueiro M et al (2018) Apple tree branches derived activated carbons for the removal of β-blocker atenolol. Chem Eng J 345:669–678. https://doi.org/10.1016/j.cej.2018.01.076
Maryam B, Buscio V, Odabasi SU, Buyukgungor H (2020) A study on behavior, interaction and rejection of paracetamol, diclofenac and ibuprofen (PhACs) from wastewater by nanofiltration membranes. Environ Technol Innov 18:100641. https://doi.org/10.1016/j.eti.2020.100641
Medana C, Calza P, Carbone F et al (2008) Characterization of atenolol transformation products on light-activated TiO2 surface by high-performance liquid chromatography/high-resolution mass spectrometry. Rapid Commun Mass Spectrom 22:301–303. https://doi.org/10.1002/rcm.3370
Mehrabadi Z, Faghihian H (2018) Comparative photocatalytic performance of TiO2 supported on clinoptilolite and TiO2/salicylaldehyde-NH2-MIL-101(Cr) for degradation of pharmaceutical pollutant atenolol under UV and visible irradiations. J Photochem Photobiol A Chem 356:102–111. https://doi.org/10.1016/j.jphotochem.2017.12.042
MiarAlipour S, Friedmann D, Scott J, Amal R (2018) TiO2/porous adsorbents: recent advances and novel applications. J Hazard Mater 341:404–423. https://doi.org/10.1016/j.jhazmat.2017.07.070
Mozgawa W (2001) The relation between structure and vibrational spectra of natural zeolites. J Mol Struct 596:129–137. https://doi.org/10.1016/S0022-2860(01)00741-4
Ohno T, Sarukawa K, Tokieda K, Matsumura M (2001) Morphology of a TiO2 photocatalyst (Degussa, P-25) consisting of anatase and rutile crystalline phases. J Catal 203:82–86. https://doi.org/10.1006/jcat.2001.3316
Oliveira RCP, Vasić M, Santos DMF et al (2018) Performance assessment of a direct borohydride-peroxide fuel cell with Pd-impregnated faujasite X zeolite as anode electrocatalyst. Electrochim Acta 269:517–525. https://doi.org/10.1016/j.electacta.2018.03.021
Olson DH, Kokotailo GT, Charnell JF (1968) The crystal chemistry of rare earth faujasite-type zeolites. J Colloid Interface Sci 28:305–314. https://doi.org/10.1016/0021-9797(68)90134-3
Pan Y, Zhang Y, Huang Y et al (2021) Synergistic effect of adsorptive photocatalytic oxidation and degradation mechanism of cyanides and Cu/Zn complexes over TiO2/ZSM-5 in real wastewater. J Hazard Mater 416:125802. https://doi.org/10.1016/j.jhazmat.2021.125802
Piedra López JG, González Pichardo OH, Pinedo Escobar JA et al (2021) Photocatalytic degradation of metoprolol in aqueous medium using a TiO2/natural zeolite composite. Fuel 284:119030. https://doi.org/10.1016/j.fuel.2020.119030
Píštková V, Tasbihi M, Vávrová M, Lavrenčič Štangar U (2015) Photocatalytic degradation of β-blockers by using immobilized titania/silica on glass slides. J Photochem Photobiol 305:19–28. https://doi.org/10.1016/j.jphotochem.2015.02.014
Ponkshe A, Thakur P (2022) Solar light-driven photocatalytic degradation and mineralization of beta blockers propranolol and atenolol by carbon dot/TiO2 composite. Environ Sci Pollut Res 29:15614. https://doi.org/10.1007/s11356-021-16796-w
Rac V, Rakić V, Stošić D et al (2020) Enhanced accessibility of active sites in hierarchical ZSM-5 zeolite for removal of pharmaceutically active substances: adsorption and microcalorimetric study. Arab J Chem 13:1945–1954. https://doi.org/10.1016/j.arabjc.2018.02.012
Radjenović J, Sirtori C, Petrović M et al (2009) Solar photocatalytic degradation of persistent pharmaceuticals at pilot-scale: kinetics and characterization of major intermediate products. Appl Catal B Environ 89:255–264. https://doi.org/10.1016/j.apcatb.2009.02.013
Rakić V, Rajić N, Daković A, Auroux A (2013) The adsorption of salicylic acid, acetylsalicylic acid and atenolol from aqueous solutions onto natural zeolites and clays: clinoptilolite, bentonite and kaolin. Microporous Mesoporous Mater 166:185–194. https://doi.org/10.1016/j.micromeso.2012.04.049
Rakić V, Rac V, Krmar M et al (2015) The adsorption of pharmaceutically active compounds from aqueous solutions onto activated carbons. J Hazard Mater 282:141–149. https://doi.org/10.1016/j.jhazmat.2014.04.062
Rodríguez-Fuentes G, Ruiz-Salvador AR, Mir M et al (1998) Thermal and cation influence on ir vibrations of modified natural clinoptilolite. Microporous Mesoporous Mater 20:269–281. https://doi.org/10.1016/S1387-1811(97)00013-9
Rueda-Márquez JJ, Palacios-Villarreal C, Manzano M et al (2020) Photocatalytic degradation of pharmaceutically active compounds (PhACs) in urban wastewater treatment plants effluents under controlled and natural solar irradiation using immobilized TiO2. Sol Energy 208:480–492. https://doi.org/10.1016/j.solener.2020.08.028
Sanganyado E, Gwenzi W (2019) Antibiotic resistance in drinking water systems: occurrence, removal, and human health risks. Sci Total Environ 669:785–797. https://doi.org/10.1016/j.scitotenv.2019.03.162
Saponjic ZV, Dimitrijevic NM, Tiede DM, Goshe AJ, Zuo X, Chen LX, Barnard AS, Zapol P, Curtiss L, Rajh T (2005) Shaping nanometer-scale architecture through surface chemistry. Adv Mater 17:965–971. https://doi.org/10.1002/adma.200401041
Shao D, Wang X, Fan Q (2009) Photocatalytic reduction of Cr(VI) to Cr(III) in solution containing ZnO or ZSM-5 zeolite using oxalate as model organic compound in environment. Microporous Mesoporous Mater 117:243–248. https://doi.org/10.1016/j.micromeso.2008.06.026
Sousa JCG, Ribeiro AR, Barbosa MO et al (2018) A review on environmental monitoring of water organic pollutants identified by EU guidelines. J Hazard Mater 344:146–162. https://doi.org/10.1016/j.jhazmat.2017.09.058
Tammaro M, Fiandra V, Mascolo MC et al (2017) Photocatalytic degradation of atenolol in aqueous suspension of new recyclable catalysts based on titanium dioxide. J Environ Chem Eng 5:3224–3234. https://doi.org/10.1016/j.jece.2017.06.026
Tayade RJ, Kulkarni RG, Jasra RV (2007) Enhanced photocatalytic activity of TiO2-coated NaY and HY zeolites for the degradation of methylene blue in water. Ind Eng Chem Res 46:369–376. https://doi.org/10.1021/ie060641o
Trujillo ME, Hirales D, Rinco ME et al (2013) TiO2/clinoptilolite composites for photocatalytic degradation of anionic and cationic contaminants. J Mater Sci 48:6778–6785. https://doi.org/10.1007/s10853-013-7482-7
Verlicchi P, Al Aukidy M, Zambello E (2012) Occurrence of pharmaceutical compounds in urban wastewater: removal, mass load and environmental risk after a secondary treatment-a review. Sci Total Environ 429:123–155. https://doi.org/10.1016/j.scitotenv.2012.04.028
Vranješ M, Šaponjić ZV, Živković LS et al (2014) Elongated titania nanostructures as efficient photocatalysts for degradation of selected herbicides. Appl Catal B Environ 160–161:589–596. https://doi.org/10.1016/j.apcatb.2014.06.005
Wilde ML, Montipó S, Martins AF (2014) Degradation of β-blockers in hospital wastewater by means of ozonation and Fe2+/ozonation. Water Res 48:280–295. https://doi.org/10.1016/j.watres.2013.09.039
Yahya N, Aziz F, Jamaludin NA et al (2018) A review of integrated photocatalyst adsorbents for wastewater treatment. J Environ Chem Eng 6:7411–7425. https://doi.org/10.1016/j.jece.2018.06.051
Yamashita H, Nose H, Kuwahara Y et al (2008) TiO2 photocatalyst loaded on hydrophobic Si3N4 support for efficient degradation of organics diluted in water. Appl Catal A Gen 350:164–168. https://doi.org/10.1016/j.apcata.2008.08.015
Yang H, An T, Li G et al (2010) Photocatalytic degradation kinetics and mechanism of environmental pharmaceuticals in aqueous suspension of TiO2: a case of β-blockers. J Hazard Mater 179:834–839. https://doi.org/10.1016/j.jhazmat.2010.03.079
Yu JG, Yu HG, Cheng B et al (2003) The effect of calcination temperature on the surface microstructure and photocatalytic activity of TiO2 thin films prepared by liquid phase deposition. J Phys Chem B 107:13871–13879. https://doi.org/10.1021/jp036158y
Zhang FZ, Guo XW, Wang XS et al (1999) Preparation and characterization of titanium-containing MFI from highly siliceous ZSM-5: effect of precursors synthesized with different templates. Mater Chem Phys 60:215–220. https://doi.org/10.1016/S0254-0584(99)00098-X
Zhang X, Wu F, Wu XW et al (2008) Photodegradation of acetaminophen in TiO2 suspended solution. J Hazard Mater 157:300–307. https://doi.org/10.1016/j.jhazmat.2007.12.098
Acknowledgements
The authors acknowledge the financial support by the Ministry of Education, Science and Technological Development of Republic of Serbia (Contract numbers: 451-03-9/2021-14/200146; 451-03-9/2021-14/200116; 451-03-9/2021-14/200051). The authors would also like to thank Associate Professor Rastko Vasilić for performing XRPD experiments.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Editorial responsibility: Senthil Kumar Ponnusamy.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Stojanović, S., Vranješ, M., Šaponjić, Z. et al. Photocatalytic performance of TiO2/zeolites under simulated solar light for removal of atenolol from aqueous solution. Int. J. Environ. Sci. Technol. 20, 1–16 (2023). https://doi.org/10.1007/s13762-022-04305-6
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13762-022-04305-6