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01-06-2020 | Thematic Issue

Photocatalytic degradation of diclofenac sodium salt: adsorption and reaction kinetic studies

Published in: Environmental Earth Sciences | Issue 11/2020

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Abstract

The photocatalytic oxidation of diclofenac, which is a non-steroidal anti-inflammatory medication, with TiO₂ illuminated with UV-A light under constant flow of pure oxygen has been investigated in our laboratories to evaluate the effect of initial reactant concentration on the reaction rate. Diclofenac adsorption experiments under dark conditions were also carried out to get information about the interaction between the organic molecule and the solid catalyst. Adsorption experiments at natural pH under dark conditions confirmed that the negatively charged diclofenac molecule is easily adsorbed on the positively charged surface of titania reaching equilibrium in less than 50 min. According to the Langmuir isotherm, the adsorption constant (K_eq) and the maximum uptake of diclofenac (q_m) on the surface of commercial TiO₂ are 21.1401 L mMol⁻¹DFC and 0.04013 mMoles DFC g⁻¹ TiO₂, respectively. Experimental results also indicate that the initial reaction rate of the photocatalytic degradation of diclofenac obeys the Langmuir–Hinshelwood–Hougen–Watson model with a kinetic constant K₁ = 0.08489 min⁻¹ and an adsorption parameter K₂ = 14.12821 mM⁻¹L. Combined chemical analysis of the reaction samples by HPLC, TOC, and UV–vis spectroscopy indicated that the diclofenac is efficiently mineralized by photocatalysis via hydroxylation of the aromatic rings to form 2-aminophenol, catechol, benzene-triol, 2,6-dichloroaniline, and fumaric acid, which in turn are completely mineralized to CO₂ and water.

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Acuña V, Ginebreda A, Mor JR, Petrovic M, Sabater S, Sumpter J, Barcelo D (2015) Balancing the health benefits and environmental risks of pharmaceuticals: diclofenac as an example. Environ Int. https://doi.org/10.1016/j.envint.2015.09.023 CrossRef

Augugliaro V, Palmisano L, Schiavello M, Sclafani A, Marchese L, Martra G, Miano F (1991) Photocatalytic degradation of nitrophenols in aqueous titanium dioxide dispersion. Appl Catal. https://doi.org/10.1016/S0166-9834(00)83310-2 CrossRef

Babić S, Horvat AJM, Mutavdžić PD, Kaštelan-Macan M (2007) Determination of pKa values of active pharmaceutical ingredients. Trends Anal Chem. https://doi.org/10.1016/j.trac.2007.09.004 CrossRef

Bekkouche S, Bouhelassa M, Salah NH, Meghlaoui FZ (2004) Study of adsorption of phenol on titanium oxide (TiO₂). Desalination. https://doi.org/10.1016/j.desal.2004.06.090 CrossRef

Bhandra BN, Ahmend I, Kim S, Jhung SH (2017) Adsorptive removal of ibuprofen and diclofenac from water using metal-organic framework-derived porous carbon. Chem Eng J. https://doi.org/10.1016/j.cej.2016.12.127 CrossRef

Bockris JOM, Otagawa T, Young V (1983) Solid state surface studies of the electrocatalysis of oxygen evolution on perovskites. J Electroanal Chem. https://doi.org/10.1016/S0022-0728(83)80243-5 CrossRef

Bonnefille B, Gomez E, Courant F, Escande A, Fenet H (2018) Diclofenac in the marine environment: a review of its occurrence and effects. Marine Poll Bull. https://doi.org/10.1016/j.marpolbul.2018.04.053 CrossRef

Boukhatem H, Khalaf H, Djouadi L, Marin Z, Navarro RM, Santaballa JA, Canle M (2017) Diclofenac degradation using mont-La (6%)-Cu_0.6Cd_0.4S as photocatalyst under NUV-Vis irradiation. Operational parameters, kinetics and mechanism. J Environ Chem Eng. https://doi.org/10.1016/j.jece.2017.10.054 CrossRef

Byrne C, Subramanian G, Pillai S (2018) Recent advances in photocatalysis for environmental applications. J Environ Chem Eng. https://doi.org/10.1016/j.jece.2017.07.080 CrossRef

Calza P, Pelizzetti E (2001) Photocatalytic transformation of organic compounds in the presence of inorganic ions. Pure Appl Chem. https://doi.org/10.1351/pac200173121839 CrossRef

Calza P, Sakkas VA, Medana C, Baiocchi C, Dimou A, Pelizzetti E, Albanis T (2006) Photocatalytic degradation study of diclofenac over aqueous TiO₂ suspensions. Appl Catal B. https://doi.org/10.1016/j.apcatb.2006.04.021 CrossRef

Chen D, Ray AK (1998) Photodegradation kinetics of 4-nitrophenol in TiO₂ suspension. Water Res. https://doi.org/10.1016/S0043-1354(98)00118-3 CrossRef

Cordero-Garcia A, Guzman-Mar JL, Hinojosa-Reyes L, Ruiz-Ruiz E, Hernandez-Ramirez A (2016) Effect of carbon doping on WO₃/TiO₂ coupled oxide and its photocatalytic activity on diclofenac degradation. Ceram Int. https://doi.org/10.1016/j.ceramint.2016.03.073 CrossRef

Czech B, Buda W (2016) Multicomponent nanocomposites for elimination of diclofenac in water based on an amorphous TiO₂ active in various light sources. J Photochem Photobiol. https://doi.org/10.1016/j.jphotochem.2016.07.024 CrossRef

De Lasa H, Serrano B, Salaices M (2005) Photocatalytic reaction engineering. Springer, New YorkCrossRef

De Oliveira T, Guégan R, Thiebault T, Le Milbeau C, Muller F, Teixeira V, Giovanela M, Boussafir M (2017) Adsorption of diclofenac onto organoclays: effects of surfactant and environmental (pH and temperature) conditions. J Hazard Mater. https://doi.org/10.1016/j.jhazmat.2016.05.0010304-3894 CrossRef

Espina de Franco M, Bonfante de Carvalho C, Marques Bonetto M, Pelegrini Soares R, Amaral Féris L (2018) Diclofenac removal from water by adsorption using activated carbon in batch mode and fixed-bed column: Isotherms, thermodynamic study and breakthrough curves modeling. J Clean Prod. https://doi.org/10.1016/j.jclepro.2018.01.138 CrossRef

Fischer K, Kuhnert M, Glaser R, Schulze A (2015) Photocatalytic degradation and toxicity evaluation of diclofenac by nanotubular titanium dioxide-PES membrane in a static and continuous setup. RSC Adv. https://doi.org/10.1039/c4ra16219f CrossRef

Fogler HS (1998) Elements of chemical reaction engineering, 4th edition, Prentice Hall, Upper Saddle River

Friedmann D, Mendive C, Bahnemann D (2010) TiO₂ for water treatment: parameters affecting the kinetics and mechanisms of photocatalysis. Appl Catal B-environ. https://doi.org/10.1016/j.apcatb.2010.05.014 CrossRef

Félix-Cañedo TE, Durán-Álvarez JC, Jiménez-Cisneros B (2013) The occurrence and distribution of a group of organic micropollutants in Mexico City's water sources. Sci Total Environ. https://doi.org/10.1016/j.scitotenv.2013.02.088 CrossRef

Gou JF, Ma QL, Cui YQ, Deng XY, Zhang HX, Cheng XW, Li XL, Xie MZ, Cheng QF, Liu HL (2017) Visible light photocatalytic removal performance and mechanism of diclofenac degradation by Ag₃PO₄ sub-microcrystals through response surface methodology. J Ind Eng Chem. https://doi.org/10.1016/j.jiec.2017.01.015 CrossRef

Herrmann J (2010) Photocatalysis fundamentals revisited to avoid several misconceptions. Appl Catal B-environ. https://doi.org/10.1016/j.apcatb.2010.05.012 CrossRef

Hines AL, Maddox RN (1985) Mass transfer: fundamentals and applications. Prentice Hall, New Jersey

Ihsanullah AHA, Saleh TA, Laoui T, Gupta VK, Atieh MA (2015) Enhanced adsorption of phenols from liquids by aluminum oxide/carbon nanotubes: comprehensive study from synthesis to surface properties. J Mol Liq. https://doi.org/10.1016/j.molliq.2015.02.028 CrossRef

Kallio JM, Lahti M, Oikari A, Kronberg L (2010) Metabolites of the aquatic pollutant diclofenac in fish bile. Environ Sci Technol. https://doi.org/10.1021/es903402c CrossRef

Kanakaraju D, Glass BD, Oelgemöller M (2014) Titanium dioxide photocatalysis for pharmaceutical wastewater treatment. Environ Chem Lett. https://doi.org/10.1007/s10311-013-0428-0 CrossRef

Kanakaraju D, Motti CA, Glass BD, Oelgemoller M (2016) Solar photolysis versus TiO₂-mediated solar photocatalysis: a kinetic study of the degradation of naproxen and diclofenac in various water matrices. Environ Sci Pollut R. https://doi.org/10.1007/s11356-016-6906-8 CrossRef

Kovacic M, Salaeh S, Kusic H, Suligoj A, Kete M, Fanetti M, Stangar UL, Dionysiou DD, Bozic AL (2016) Solar-driven photocatalytic treatment of diclofenac using immobilized TiO₂-based zeolite composites. Environ Sci Pollut R. https://doi.org/10.1007/s11356-016-6985-6 CrossRef

Larous S, Meniai AH (2013) Elimination of organic pollutants from wastewater. Application to p-nitrophenol, Desalin. Water Treat. https://doi.org/10.1080/19443994.2013.795716 CrossRef

Larous S, Meniai AH (2016) Adsorption of diclofenac from aqueous solution using activated carbon prepared from olive stones Int. J Hydrog Energy. https://doi.org/10.1016/j.ijhydene.2016.01.096 CrossRef

Levenspiel O (1998) Chemical reaction engineering, 3rd edn. Wiley, New York

Leyva E, Moctezuma E, Lopez M, Baines KM, Zermeño B (2019) Photocatalytic degradation of β-blockers in TiO₂ with metoprolol as model compound. Intermediates and total reaction mechanism. Catal Today. https://doi.org/10.1016/j.cattod.2018.08.007 CrossRef

Leyva E, Moctezuma E, Noriega S (2017) Photocatalytic degradation of omeprazole intermediates and total reaction mechanism. J Chem Technol Biotechnol. https://doi.org/10.1002/jctb.5263 CrossRef

Li X, Cubbage JW, Jenks WS (1999) Photocatalytic degradation of 4-chlorophenol. 2. The 4-chlorocatechol pathway. J Org Chem. https://doi.org/10.1021/jo990912n CrossRef

Litter MI (1999) Heterogeneous photocatalysis—transition metal ions in photocatalytic systems. Appl Catal B. https://doi.org/10.1016/S0926-3373(99)00069-7 CrossRef

Lonappan L, Kaur Brar S, Das RK, Verma M, Surampalli RY (2016) Diclofenac and its transformation products: environmental occurrence and toxicity—a review. Environ Int. https://doi.org/10.1016/j.envint.2016.09.014 CrossRef

Lonappan L, Rouissi T, Kaur-Brar S, Verma M, Surampalli RY (2018) An insight into the adsorption of diclofenac on different biochars: mechanisms, surface chemistry and thermodynamics. Bioresour Technol. https://doi.org/10.1016/j.biortech.2017.10.039 CrossRef

Loosli F, Le Costumer P, Stoll (2015) Impact of alginate concentration on the stability of agglomerates made of TiO₂ engineered nanoparticles: water hardness and pH effects. J Nanopart Res. https://doi.org/10.1007/s11051-015-2863-2 CrossRef

Martinez C, Canle M, Fernandez MI, Santaballa JA, Faria J (2011) Aqueous degradation of diclofenac by heterogeneous photocatalysis using nanostructured materials. Appl Catal B. https://doi.org/10.1016/j.apcatb.2011.07.003 CrossRef

Martínez-de la Cruz A, Obregón Alfaro S (2009) Synthesis and characterization of nanoparticles of α-Bi₂Mo₃O₁₂ prepared by co-precipitation method: langmuir adsorption parameters and photocatalytic properties with rhodamine B. Solid State Sci. https://doi.org/10.1016/j.solidstatesciences.2009.01.007 CrossRef

Medina-Valtierra J, Frausto-Reyes C, Ramirez-Ortiz J, Moctezuma E, Ruiz F (2007) Preparation of rough anatase films and the evaluation of their photocatalytic efficiencies. Appl Catal B. https://doi.org/10.1016/j.apcatb.2007.05.033 CrossRef

Michael I, Achilleos A, Lambropoulou D, Torrens VO, Perez S, Petrovic M, Barcelo D, Fatta-Kassinos D (2014) Proposed transformation pathway and evolution profile of diclofenac and ibuprofen transformation products during (sono)photocatalysis. Appl Catal B. https://doi.org/10.1016/j.apcatb.2013.10.035 CrossRef

Moctezuma E, Leyva E, Aguilar CA, Luna RA, Montalvo C (2012) Photocatalytic degradation of paracetamol: Intermediates and total reaction mechanism. J Hazard Mater. https://doi.org/10.1016/j.jhazmat.2012.10.010 CrossRef

Moctezuma E, Leyva E, Lopez M, Pinedo A, Zermeno B, Serrano B (2013) Photocatalytic degradation of metoprolol tartrate. Top Catal. https://doi.org/10.1007/s11244-013-0119-x CrossRef

Moctezuma E, Leyva E, Palestino G, de Lasa (2007) Photocatalytic degradation of methyl parathion: reaction pathways and intermediate reaction products. J Photochem Photobiol A. https://doi.org/10.1016/j.jphotochem.2006.07.014 CrossRef

Moctezuma E, Zamarripa H, Leyva E (2003) Degradación fotocatalítica de soluciones de alta concentración de paraquat. Rev Int Contam Ambient 19(3):117–125

Moreno-Valencia EI, Paredes-Carrera SP, Sanchez-Ochoa JC, Flores-Valle SO, Avendano-Gomez JR (2017) Diclofenac degradation by heterogeneous photocatalysis with Fe₃O₄/TixOy/activated carbon fiber composite synthesized by ultrasound irradiation. Mater Res Express. https://doi.org/10.1088/2053-1591/aa981f CrossRef

Nakata K, Fujishima A (2012) TiO₂ photocatalysis: design and applications. J Photochem Photobiol C. https://doi.org/10.1016/j.jphotochemrev.2012.06.001 CrossRef

Oaks JL, Gilbert M, Virani MZ, Watson RT, Meteyer CU, Rideout BA, Shivaprasad HL, Ahmed S, Chaudhry MJI, Arshad M, Mahmood S, Ali KAA (2004) Diclofenac residues as the cause of vulture population decline in Pakistan. Nature. https://doi.org/10.1038/nature02317 CrossRef

Okamoto K, Yamamoto Y, Tanaka H, Itaya A (1985) Kinetics of heterogeneous photocatalytic decomposition of pPhenol over anatase TiO₂ powder. Bull Chem Soc Jpn 58:2023–2028CrossRef

Perez-Estrada LA, Maldonado MI, Gernjak W, Aguera A, Fernandez-Alba AR, Ballesteros MM, Malato S (2005) Decomposition of diclofenac by solar driven photocatalysis at pilot plant scale. Catal Today. https://doi.org/10.1016/j.cattod.2005.03.013 CrossRef

Perisic DJ, Gilja V, Stankov MN, Katancic Z, Kusic H, Stangar UL, Dionysiou DD, Bozic AL (2016) Removal of diclofenac from water by zeolite-assisted advanced oxidation processes. J Photochem Photobiol A 1:1. https://doi.org/10.1016/j.jphotochem.2016.01.030 CrossRef

Pinedo A, Lopez M, Leyva E, Zermeño B, Serrano B, Moctezuma E (2016) Photocatalytic decomposition of metoprolol and its intermediate organic reaction products: kinetics and degradation pathway. Int J Chem React Eng. https://doi.org/10.1515/ijcre-2015-0132 CrossRef

Ryu J, Choi W (2008) Substrate-specific photocatalytic activities of TiO₂ and multiactivity test for water treatment application. Environ Sci Technol. https://doi.org/10.1021/es071470x CrossRef

Sabzehmeidani MM, Karimi H, Ghaedi M (2018a) Electrospinning preparation of NiO/ZnO composite nanofibers for photodegradation of binary mixture of rhodamine B and methylene blue in aqueous solution: central composite optimization. Appl Organomet Chem. https://doi.org/10.1002/aoc.4335 CrossRef

Sabzehmeidani MM, Karimi H, Ghaedi M (2018b) Sonophotocatalytic treatment of rhodamine B using visible-light-driven CeO₂/Ag₂CrO₄ composite in a batch mode based on ribbon-like CeO₂ nanofibers via electrospinning. Environ Sci Pollut R. https://doi.org/10.1007/s11356-019-04253-8 CrossRef

Saleh TA (2017) Advanced nanomaterials for water engineering, treatment and hydraulics. IGI-Global, HersheyCrossRef

Saleh TA, Saria A, Tuzen M (2017b) Optimization of parameters with experimental design for the adsorption of mercury using polyethylenimine modified-activated carbon. J Environ Chem Eng. https://doi.org/10.1016/j.jece.2017.01.032 CrossRef

Saleh TA, Tuzen M, Sari A (2017a) Magnetic activated carbon loaded with tungsten oxide nanoparticles for aluminum removal from waters. J Environ Chem Eng. https://doi.org/10.1016/j.jece.2017.05.038 CrossRef

Santos L, Araujo AN, Fachini A, Pena A, Delerue-Matos C, Montenegro M (2010) Ecotoxicological aspects related to the presence of pharmaceuticals in the aquatic environment. J Hazard Mater. https://doi.org/10.1016/j.jhazmat.2009.10.100 CrossRef

Sarasidis VC, Plakas KV, Patsios SI, Karabelas AJ (2014) Investigation of diclofenac degradation in a continuous photo-catalytic membrane reactor. Influence of operating parameters. Chem Eng J. https://doi.org/10.1016/j.cej.2013.11.026 CrossRef

Sauer T, Neto GC, Jose HJ, Moreira R (2002) Kinetics of photocatalytic degradation of reactive dyes in a TiO₂ slurry reactor. J Photochem Photobiol A. https://doi.org/10.1016/S1010-6030(02)00015-1 CrossRef

Shi JW, Wang ZY, He C, Wang HK, Chen JW, Fu ML, Li GD, Niu CM (2015) CdS quantum dots modified N-doped titania plates for the photocatalytic mineralization of diclofenac in water under visible light irradiation. J Mol Catal A. https://doi.org/10.1016/j.molcata.2015.01.030 CrossRef

Sun K, Shi Y, Wang X, Li Z (2017) Sorption and retention of diclofenac on zeolite in the presence ofcationic surfactant. J Hazard Mater. https://doi.org/10.1016/j.jhazmat.2016.08.0260304-3894 CrossRef

Turki A, Guillard C, Dappozze F, Ksibi Z, Berhault G, Kochkar H (2015) Phenol photocatalytic degradation over anisotropic TiO₂ nanomaterials: kinetic study, adsorption isotherms and formal mechanisms. Appl Catal B. https://doi.org/10.1016/j.apcatb.2014.08.010 CrossRef

Verlicchi P, Al Aukidy M, Galletti A, Petrovic M, Barceló D (2012) Hospital effluent: Investigation of the concentrations and distribution of pharmaceuticals and environmental risk assessment. Sci Total Environ. https://doi.org/10.1016/j.scitotenv.2012.04.055 CrossRef

Vieno N, Sillanpää M (2014) Fate of diclofenac in municipal wastewater treatment plant—a review. Environ Int. https://doi.org/10.1016/j.envint.2014.03.021 CrossRef

Zhang G, Kim G, Choi W (2014) Visible light driven photocatalysis mediated via ligand-to-metal charge transfer (LMCT): an alternative approach to solar activation of titania. Energy Environ Sci. https://doi.org/10.1039/c3ee43147a CrossRef

Zhang W, Zhou L, Deng HP (2016) Ag modified g-C₃N₄ composites with enhanced visible-light photocatalytic activity for diclofenac degradation. J Mol Catal A-Chem. https://doi.org/10.1016/j.molcata.2016.07.021 CrossRef

Title: Photocatalytic degradation of diclofenac sodium salt: adsorption and reaction kinetic studies
Publication date: 01-06-2020
Published in: Environmental Earth Sciences / Issue 11/2020
Print ISSN: 1866-6280
Electronic ISSN: 1866-6299
DOI: https://doi.org/10.1007/s12665-020-09017-z

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