Photodegradation of Ibuprofen, Cetirizine, and Naproxen by PAN-MWCNT/TiO2–NH2 nanofiber membrane under UV light irradiation
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In this study, the photodegradation of three pharmaceuticals, namely Ibuprofen (IBP), Naproxen (NPX), and Cetirizine (CIZ) in aqueous media was investigated under UV irradiation. The photocatalyst used in this work consists of surface functionalized titanium dioxide (TiO2–NH2) nanoparticles grafted into Polyacrylonitrile (PAN)/multi-walled carbon nanotube composite nanofibers. Surface modification of the fabricated composite nanofibers was illustrated using XRD, FTIR, and SEM analyses.
Sets of experiments were performed to study the effect of pharmaceuticals initial concentration (5–50 mg/L), solution pH (2–9), and irradiation time on the degradation efficiency. The results demonstrated that more than 99% degradation efficiency was obtained for IBP, CIZ, and NPX within 120, 40, and 25 min, respectively.
Comparatively, the photocatalytic degradation of pharmaceuticals using PAN-CNT/TiO2–NH2 composite nanofibers was much more efficient than with PAN/TiO2–NH2 composite nanofibers.
KeywordsPhotocatalytic Cetirizine Naproxen Ibuprofen Composite nanofibers UV-light
multi-walled carbon nanotube
Scanning Electron Microscopy
Fourier transform infrared spectroscopy
Nowadays, the world recognizes the importance of the continuous development on the area of synthesis and production of a variety of pharmaceutical drugs for both humans and animals. Large scales of different chemical compounds are used as medicinal products. These compounds classified as emerging pollutants, while their essential passage into the environment is pharmaceutical industries, excretory products of medically treated humans and animals, which followed by their inefficient removal in wastewater treatment plants [1, 2]. Also they enter to the environment after inappropriate disposal of expired pharmaceutical products in the sewage system or in the garbage. The extended usage of dangerous pharmaceuticals is followed by an increased pollution of ground, surface, and drinking water by these compounds [3, 4].
The most considerably detected groups of pharmaceuticals in the environment are Non-steroidal anti-inflammatory drugs (NSAIDs). These are one of the widely available drugs in the world. NSAID group have a main common characteristic, which is the carboxylic aryl acid moiety, which provides their acidic properties. Ibuprofen (IBP) belongs to this family of pharmaceuticals, which is an analgesic drug highly used for the medicament of myoskeletal injuries, rheumatoid arthritis, and fever . A large number of NSAIDs are widely existing in surface water, these contaminations are highly problematic because the surface waters are main resources used for drinking water production. Choina et al. , studied the degradation of the IBP and the results indicated that the photocatalytic treatment with titania catalyst leads to rapid mineralization of ibuprofen. NPX also belongs to the non-steroidal anti-inflammatory drug (NSAID) . In addition, NPX is used as an antipyretic and analgesic drug for the treatment of rheumatoid arthritis. In addition, it is also used as veterinary medicine . Ray et al. , studied the degradation of the NPX over AgBr-α-NiMoO4 composite photocatalyst and the results show that the composite photocatalyst degraded NPX drug rapidly within 20 min under visible light irradiation. The photocatalytic performances of composite stayed efficient up to fifth cycle, and this indicates to the excellent stability [10, 11]. Moreover, CIZ append to the piperazine class of second generation antihistamines used in the treatment of allergies, hay fever, angioedema, and urticarial and causes various side effects such as dry mouth, sleepiness, sedation, fatigue, fever, stomach upset, and blurred vision when ingested accidentally to the human body . The degradation of CIZ has not reported neither by enzymatic method nor by ultrasound assisted enzymatic method. Rahul et al. , studied the degradation of the CIZ using a novel technique of laccase enzyme as a catalyst under the influence of ultrasound irradiation. The results show that the degradation of CIZ achieved was 91% in comparison of ultrasound assisted enzymatic degradation with conventional at a shorter time.
The most conventional treatment processes applied at domestic wastewater treatment plants fail to remove completely pharmaceutical substances. Therefore, the treatment of the polluted water requires the application of effective techniques such as Advanced Oxidation Processes (AOPs) [14, 15]. Among AOPs, photocatalysis is a very important and attractive process. Heterogeneous photocatalytic water treatment has a highly special interest since it doesn’t require the use of any additional chemicals [16, 17]. The photocatalytic processes mainly use semiconducting material catalysts such as (TiO2, Fe2O3, ZnO) under light exposure (UV-light or sunlight) to degrade the organic and inorganic contaminants. Most of the researches are now focusing on the photocatalytic techniques using composite nanofibers [18, 19]. Many semiconducting catalysts can be used, but Titania (TiO2) is the most common semiconducting catalyst used due to its cheap cost combined with a high photocatalytic activity, nonhazardous compound and eco-friendly [20, 21]. The application of Titania catalyst is most attractive for effective photocatalytic degradation of drugs and other harmful organic pollutants assisted by UV–Vis radiation. In this work, PAN nanofibers were used as substrate for holding the photocatalyst material. On the other hand, MWCNTs was used to improve the tensile strength, young’s modulus, and chemical resistance of the nanofiber due to their high physical, and chemical properties [22, 23, 24]. In addition, CNT may increases the photocatalytic activity of the process due to its electron donor properties. Moreover, it offers the possibility of complete abatement of drugs and can be recovered and re-used [25, 26]. Therefore, the aim of this work was to investigate the photodegradation of IBP, NPX, and CIZ in aqueous media by means of composite nanofibers (PAN-MWCNT/TiO2–NH2) under UV irradiation. The effect of operating conditions such as initial drug concentration, and solution pH were evaluated.
Composite nanofibers preparation
A 10 wt% solution of PAN powder in DMF was prepared by mixing 1 g PAN with 9 mL DMF for 4 h at 50 °C. In parallel, 3 wt% surface activated MWCNTs were dispersed in DMF; the dispersion was stirred for 15 min, and then sonicated for 30 min. PAN solution was then added to the MWCNTs. The mixture was magnetically stirred for 15 min and then sonicated for 3 h. The electrospinning process was conducted at room temperature using a voltage of 25 kV, flow rate of 0.5 ml/h, and distance from needle tip to collector was 15 cm . The electrospun PAN/MWCNT nanofibers were dried in vacuum over night to remove the excess amount of solvent. The electrospun composite nanofibers was cross-linked to TiO2–NH2 NPs. The composite nanofibers was then immersed in the crosslinking medium, which consisting of 100 mL distilled water and 2.5 wt% GA and placed in a mechanical shaker for 24 h at the room temperature. After the crosslinking process the composite nanofibers was washed with deionized water. The surface functionalization TiO2–NH2 NPs was suspended in 5 mL deionized water, afterward sonicated for 2 h and then added to the cross-linked composite nanofibers and mixed using mechanical shaker for 24 h. The PAN-CNT/TiO2–NH2 composite nanofibers was finally washed with deionized water and dried in air at the room temperature.
The morphology of the composites nanofibers was examined using Scanning Electron Microscopy (SEM, Gemini Zeiss-Ultra 55). Fourier transform infrared spectroscopy (FTIR, Nicolet iS10) was used to confirm the presence of amino groups on the TiO2 NPs attached to the surface of the composite nanofibers. The crystal phases of the composite nanofibers were evaluated by X-ray diffractometry (XRD, Bruker D8) using Cu Kα radiation (λ = 1.5406 Å). The concentration of IBP, NPX, and CTZ in the solution was measured using UV–Vis/NIR spectrophotometer (model LAMBDA 750, Perkin Elmer) at maximum absorption wavelength (λmax) 222 nm, 229 nm and 232 nm for IBP, CTZ, and NPX, respectively.
Results and discussion
Effect of catalyst amount
Effect of exposure time
Effect of drug initial concentration
The Effect of the pH of the solution
Characterization of the composite nanofibers
TiO2–NH2 NPs were successfully cross-linked to the PAN/MWCNT composite nanofibers. This study demonstrated that the fabricated composite nanofibers PAN-MWCNT/TiO2–NH2 is an effective photocatalyst for the degradation of IBP, NPX, and CIZ in aqueous solutions under UV-light. Operational parameters, such as initial drug concentration, catalyst amount, irradiation time, and solution pH were investigated. It was shown that the complete degradation can be achieved at low drug concentration (5 mg/L), acidic pH = 2, and at a low power intensity of the UV lamp (40 Watt). The complete photodegradation of IBP, NPX, and CIZ required 120, 40, and 25 min, respectively. The stability studies showed that the photodegradation efficiency of PAN-MWCNT/TiO2–NH2 composite nanofibers remained stable under the experimental conditions studied.
AM, AS, and WN conceived, designed, and performed the experiments; AM and AS analyzed the data and wrote the paper; AU reviewed, edited, and approved the manuscript. All authors read and approved the final manuscript.
The authors declare that they have no competing interests
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