Visible light Induced Photocatalytic Activity of Polypyrrole Decorated Zinc Ferrite Green Nanohybrids Against Cetirizine Hydrochloride Degradation

Visible light Induced Photocatalytic Activity of Polypyrrole Decorated Zinc Ferrite Green Nanohybrids Against Cetirizine Hydrochloride Degradation | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Visible light Induced Photocatalytic Activity of Polypyrrole Decorated Zinc Ferrite Green Nanohybrids Against Cetirizine Hydrochloride Degradation shayista Gaffar, elham S Aazam, ufana riaz This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3955347/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 01 Nov, 2024 Read the published version in Environmental Science and Pollution Research → Version 1 posted 5 You are reading this latest preprint version Abstract The present work reports photocatalytic degradation of cetirizine hydrochloride (CTZ-HCl) utilizing polypyrrole (PPy) nanohybrids with ZnFe 2 O 4 (ZnFe) nanoparticles. The synthesized materials were characterized using UV-Visible spectroscopy, X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), Photoluminescence (PL) spectroscopy, BET and scanning electron microscopy (SEM) techniques. IR and XRD analysis confirmed the formation of ZnFe/PPy nanohybrids. UV reflectance studies revealed that the band gap was found to decrease with increase in the loading of PPy and Kubelka -Munk plots confirmed the bandgap values to be 2.03 eV for ZnFe, 1.94 eV for 1% PPy/ZnFe, 1.66 eV for 3% PPy/ZnFe and 1.38 eV for 5% PPy/ZnFe. The photocatalytic performance against CTZ-HCl degradation was performed under visible light irradiation for 60 min. The effect of catalyst dosage and the effect of drug concentration were investigated to confirm degradation behavior of the PPy/ZnFe photocatalysts. The degradation followed the pseudo first order kinetics model. Maximum photocatalytic degradation was observed to be 98% within 60 minutes using 5% PPy/ZnFe as the photocatalyst. The recyclability tests revealed that the 5% PPy/ZnFe photocatalyst was reusable up to 4 cycles. Radical scavenging studies confirmed the generation of ● OH radicals that were responsible for the drug degradation. The degraded fragments were analyzed using LCMS technique and the tentative mechanism of degradation was proposed. cetirizine hydrochloride antihistamine polypyrrole photocatalysis Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 1. Introduction The release of pollutants into water bodies has increased during the past few decades as a result of the rapid development of contemporary society ( Mar-Ortiz et al. 2020 ). Numerous pollutants are found in waste water from industries, medical facilities, and households. These pollutants pass through aquatic environments and have a negative impact on aquatic life ( Szkoda et al. 2020 ,Oliva et al. 2020 ). Pesticides, dyes, and medications are among the contaminants that are of the utmost significance ( Ethiraj et al. 2020 ,Yuan et al. 2021 ). The discharge of pharmaceutical products in ground water, surface water, and drinking water leads to accumulation of antibiotics, anti-inflammatory drugs, psychiatric drugs, analgesics, and antihistamines. A report from the united nations has estimated that 1500 km 3 of wastewater are produced annually, of which over 70% is discharged into freshwater sources untreated, contributing to the serious problem of water pollution ( Stricker 1988 ,Souri et al. 2013 ) . Cetirizine hydrochloride is a drug from the antihistamine category that is found in numerous water sources. 2-(2-(4-(4-chlorophenyl) phenyl methyl) piperazin-1-yl) ethoxy) acetic acid di hydrochloride is the chemical name for cetirizine hydrochloride ( Zhu et al. 2022 ). It is a second-generation antihistamine belonging to the piperazine category that is employed for treating urticaria, allergic rhinitis, edoema, and allergies. In many parts of the world, cetirizine hydrochloride (CTZ-HCl) is now recognized as a significant contaminant ( Petrie et al. 2015 , Sutar and Rathod 2015 ) . In reaction to repeated or prolonged exposure to CTZ-HCl at greater concentrations, numerous harmful cumulative consequences have been observed ( Mohamed et al. 2018 ). Few experiments have been conducted to remove this contaminant from water sources ( Souri et al. 2013 , Zhu et al. 2022 ). Among the physical and chemical techniques utilized for water remediation, photo-catalytic degradation offers a number of advantages due to its potential effectiveness in degrading the contaminants under light irradiation without causing secondary pollution ( Gaffar et al. 2023a , Gaffar et al. 2023c , Zia et al. 2020 ,Zia et al. 2021 ). Metal ferrites (MFe 2 O 4 ) are ferromagnetic materials that have been used in a variety of applications because of their unique magnetic, optical, and electrical characteristics ( Dippong 2021 ,Gaffar et al. 2023b ,Makofane et al. 2021 ). These substances have found widespread use as catalysts, medication delivery systems, pigments, sensors, fluids, magnetic recording, and other functions ( Chamani et al. 2022 ,Jeseentharani et al. 2013 ). One of the most extensively researched ferrites for photocatalytic and photo electro catalytic uses is zinc ferrite, or ZnFe 2 O 4 ( Sato et al. 1990 , Boumaza et al. 2010 ). Conducting polymers (CPs) are known as sensitizers which play a vital role in the reduction of band gap of various metal oxides(Zia and Riaz 2020 )(Kashyap et al. 2018 )(Zia et al. 2019 ). Das et al . (Das et al. 2020 ) have studied the photocatalytic activities of polypyrrole sensitized zinc ferrite/graphitic carbon nitride n-n Heterojunction towards Ciprofloxacin Degradation (92%). Ashraf et al . ( Ashraf et al. 2023 ) utilized the polypyrrole/ zinc ferrite nanocomposites for the removal of Red X-GRL and direct sky-blue dyes from waste-water. However, no work has been done on degradation of CTZ-HCl by zinc Ferrites. In our recent work, we have investigated the microwave-assisted rapid catalytic degradation of isoniazid drug using polythiophene/ZnFe 2 O 4 organic-inorganic hybrids ( Gaffar et al. 2023c ). The degradation mechanism was proposed to be the generation of hotspots under microwave irradiation. The microwave technique does not consider the band gap of the ferrites. Hence in this study, we have explored the ban dgap variation of ZnFe upon interaction with PPy and its photocatalytic activity under visible light irradiation. The synthesized nano materials were characterized for their spectral, thermal, and morphological properties. Based on radical scavenging experiments and LCMS studies, the mechanism of degradation was hypothesized. 2. Materials and Methods Zinc chloride (ZnCl 2 ), (136.286 g/mol, ≥ 99.995% trace metals basis, Merck, India), ferric chloride hexahydrate (FeCl 3 ·6H 2 O) (270.294 g/mol, ≥ 98.995% trace metals basis Sigma-Aldrich, USA), pyrrole (C 4 H 5 N) (67.09 g/mol, 98%, Loba Chemie Pvt. Ltd, India), ammonium hydroxide solution ( 28% NH 3 in H 2 O, ≥ 99.99% trace metals basis, Sigma Aldrich ,USA) ethylene diamine tetra acetic acid (EDTA) (HO 2 CCH 2 ) 2 NCH 2 CH 2 N(CH 2 CO 2 H), (372.24 g/mol, Merck, India), benzoquinone (C 6 H 4 O 2 ) (108.09 g/mol Merck, India), isopropyl alcohol (C 3 H 8 O) (≥ 99.7%, Merck, India), methanol (≥ 99.6%, Sigma-Aldrich, USA), ethanol (≥ 99.7% Merck, India) and distilled water were used without further purification. Cetirizine hydrochloride (C 21 H 25 ClN 2 O 3 ·2HCl) (molecular weight 461.8 g/mol) was obtained from Sigma Aldrich. 2.1 Synthesis of PPy/ZnFe nanohybrids ZnFe 2 O 4 (ZnF) nanoparticles were synthesized as per method reported in our earlier studies ( Gaffar et al. 2023c ). The synthesized ZnFe 2 O 4 and pyrrole monomer were added together in a 150 ml conical flask containing 60 ml methanol: water mixture (30 ml v/v) and the mixture was sonicated at 25°C on ultrasonic bath (30 kHz) for 30 min. Ferric chloride dissolved in 30 ml was added to the above reaction mixture monomer oxidant ratio (1:1) and was then exposed to further sonication for about 4 h. The synthesized nanohybrids were filtered and washed several times with distilled water and dried in vacuum oven for 24h at 80°C. On the basis of the weight ratios of the ferrite/monomer used, the nanohybrids were designated as 1% PPy/ZnFe, 3% PPy/ZnFe and 5% PPy/ZnFe. 3. Characterization 3.1 Spectral Analysis Shimadzu IR Affinity-1 FT-IR spectrophotometer was used to capture the FT-IR spectra of ZnFe and PPy/ZnFe nanohybrids. In the form of KBr pellets, spectra with frequencies in the range of 400 to 4000 cm − 1 were captured. Diffuse reflectance spectroscopy (Perkin-Elmer Lamda-30) was used to measure the UV-Vis reflectance spectra of synthetic materials. The wave length ranged from 200 to 800 nm. 3.2 Morphological Analysis On a Philips Pw-3710 X-ray diffractometer using Ni-filtered Cu-K radiation, the X-ray diffraction patterns of ZnFe and PPy/ZnFe nanohybrids were obtained. Field emission-scanning electron microscopy (FE-SEM) was used to analyze the morphology (Leo Supra 50 V P, Carl Zeiss, Germany). 3.3 BET studies The BET (Brunauer–Emmett–Teller) -specific surface area was calculated at P/P0 = 0.05–0.25, and the pore size distribution and volume were derived from the adsorption branch by using the Barrett–Joyner–Halenda (BJH) mode. 3.4 Photoluminescence studies Room-temperature photoluminescence (PL) measurements were carried out with excitation by a 325 nm line of a He–Cd laser to evaluate the optical property of ZnFe and its nanohybrid with PPy. 3.5 Photocatalytic Activity Photocatalytic activities were carried out in the presence of visible light by breaking down CTZ-HCl using a 500-watt halogen lamp. Approximately 150 mg of catalyst was dispersed in 300 ml of CTZ-HCl solution and the adsorption-desorption equilibrium between the CTZ-HCl solution and the catalyst was established by keeping it under dark condition for 3 hours. The solution was then exposed to visible light irradiation for 60 minutes, and at regular intervals of 0, 10, 20, 30, 40, 50, and 60 minutes, aliquots of the solution (5 ml) were taken from the solution and centrifuged. The UV spectra of the CTZ-HCl were captured using a Perkin-Elmer Lambda 30 type UV-Vis spectrophotometer. Cetirizine hydrochloride's λ max values were measured at a wavelength of 229 nm. 3.6 Scavenging Experiments and Recyclability tests We were able to investigate the reactive species that were responsible for the degradation process by using 5mM concentrations of the scavengers isopropyl alcohol (IPA) for the detection of ● OH radicals, ethylene diamine tetra acetate (EDTA) for the detection of holes (h + ), and benzoquinone for the detection of electrons (e − ) ( Gaffar et al. 2023a ,Gaffar et al. 2023c ). They were gradually introduced to the catalyst-containing cetirizine hydrochloride solution to observe how scavengers affected the rate of degradation. The recyclability of ZnFe and 5% PPy/ZnFe nanohybrids were demonstrated in the photocatalytic degradation procedure up to five cycles. ZnFe and 5% PPy/ZnFe were collected at the end of every cycle. The collected samples were washed with distilled water and dried in vacuum oven for about 6 h at 80 o C. 3.7 Analysis of degraded fragments For detection and identification of degradation products, liquid chromatography-mass spectroscopy (LC-MS) was conducted using a Finnigan LCQ ion trap mass spectrometer equipped with an electro spray ionization interface (ESI) source and operated in 10 negative polarity mode fitted with a Genesis, C-18 column (4.6×250mm) containing 4 µm packed particles (Alltech, Deerfield, Germany).The gradient HPLC separation was coupled with LC/MSD trap 6310, ion trap mass spectrometer (Agilent technologies). The experiments were carried out in triplicate for evaluating the effect of nanohybrid catalyst dosage and initial dye concentration in the degradation of MG. Mineralization of the dye was determined by measuring the total organic content (TOC) of the degraded dye at 10–60 minutes on Shimadzu TOC-5000A total organic carbon analyzer. 4. Results and Discussion 4.1 SEM analysis The morphology of obtained ZnFe and PPy/ZnFe nanohybrids has been analyzed using SEM analysis displayed in Fig. 1 (a-d). The SEM of ZnFe revealed intense bright, flower-like morphology with rough surface ( Rahman et al. 2023 ). The SEM of 1% PPy/ZnFe and 3% PPy/ZnFe, Fig. 1 (b),(c) showed the formation of heterogeneous morphology with globular spherical aggregates of dark particles associated with PPy embedded with bright nodular particles which were correlated to ZnFe. The size of dark PPy particles was small but the distribution of the dark particles increased with the increasing in PPy confirming that the hybrid was heterogeneous and revealed mixed morphology. The SEM micrograph of 5% PPy/ZnFe, Fig. 1 (d), showed the formation of huge spherical clusters of dark and bright particles. The morphology clearly shows that huge structural transformation occurs upon increase of loading of PPy. 4.2 IR analysis The FTIR spectra of as synthesized ZnFe and PPy/ZnFe nanohybrids are shown in Fig. 2 (a-d). The broad band absorption peak at 3415 cm − 1 in ZnFe ,Fig. 2 (a) was due to the presence of OH group of entrapped water. The peak at 1684 cm − 1 was attrivutred to the metal-OH (M-OH) stretching vibration. Zn-O vibration was indicated by the presence of the peak at 846 cm − 1 . The peak at 657 cm − 1 was attributed to Fe-O vibration, and represent the tetrahedral and octahedral modes of Fe in ZnFe. The existence of the peaks above supported the formation of ZnFe ( Gaffar et al. 2023c ,Zia et al. 2020 ). In case of 1% PPy/ZnFe nanohybrid, Fig. 2 (b), the peak at 3309 cm − 1 corresponded to the NH and OH stretching vibration of PPy and entrapped water respectively. The peaks at 1556 cm − 1 and 1408 cm − 1 were attributed to the C = N bands of pyrrole. The peak at 1197 cm − 1 corresponded to N- C bending vibration of PPy. The peaks at 1043 cm − 1 was attributed to C-H stretching vibration of PPy, while the peak associated with pyrrole ring appeared at 927 cm − 1 . The IR spectrum of 3% PPy/ZnFe, Fig. 2 (c), showed characteristic peak at 3148 cm − 1 representing –OH and NH stretching vibration peaks. The peaks at 1546 cm − 1 and 1402 cm − 1 corresponds to C = N bands of pyrrole ring vibrations and the peak at 1192 cm − 1 was observed representing N-C bending vibration. The peaks at 1045 cm − 1 and 921 cm − 1 were also observed corresponding to = C-H in plane vibration and N-H in plane vibrations of pyrrole ring. Similarly, the IR spectrum of 5% PPy/ZnFe, Fig. 2 (d), was also recorded displaying the characteristic peak at 3142 cm − 1 representing the –OH stretching of H 2 O and NH of pyrrole. The peaks at 1550 cm − 1 , 1402 cm − 1 and 1195 cm − 1 were seen corresponding to C = C bands, N-H stretching vibration of pyrrole ring and N-C stretch vibration respectively. The peak at 1045 cm − 1 represented = C-H in plane vibration. The peak at 923 cm − 1 was also observed corresponding to N-H in plane vibrations (Zia and Riaz 2020 ) . The region of NH/OH stretching vibration appeared to be broad and intense confirming the interaction of NH of pyrrole with the M-OH of ZnFe. The presence of the peaks associated with ZnFe and with PPy therefore confirmed the formation of the nanohybrid. 4.3 XRD analysis The XRD profile of ZnFe and PPy/ZnFe nanohybrids are depicted in Figure 3. The XRD profile of ZnFe demonstrated peaks at 2θ= 27.46°, 31.7°, 45.3°,56.3° and 74.9° which correspond to (220), (311), (400), (422), (511), and (533) crystal planes respectively. The cubic spinel structure precisely corresponded to all of the peaks described by JCPD card no. 01‐077‐ 0011 (Algarni et al. 2022) . The 1% PPy/ZnFe nanohybrid revealed diffraction peaks at 2θ= 18.06°, 31.5°, 35.08°, 56.46° and 61.7° corresponding to crystal planes (200), (220), (311), (511) and (533) respectively. For 3% PPy/ZnFe demonstrated crystal planes (200), (220), (311), (511) and (533) revealed by diffraction peaks at 2θ =18.06°, 31.5°, 35.08°, 56.46° and 61.7° respectively. The nanohybrid 5% PPy/ZnFe revealed peaks at 2θ = 12.62°, 18.34°, 31.5°, 35.22°, 56.46° and 61.9° corresponding to crystal planes (001), (200), (220), (311), (511) and (533) respectively. The peaks that were previously seen in pure ZnFe and which correlate to different crystal planes have been retained in the nanohybrids 1% PPy/ZnFe, 3% PPy/ZnFe, and 5% PPy/ZnFe. The peak intensities of ZnFe were found to show broadening when PPy loading was increased from 1–5%, confirming that the nanohybrid transformed into a semi-crystalline state. The structural changes appeared presumably due to the encapsulation by PPy chains that tend to arrange themselves along the ZnFe planes causing the later to be semi-crystalline. 4.4 Photoluminescence studies The Fig. 4 displays the room temperature PL spectrum of ZnFe and 5% PPy/ZnFe 2 O 4 nanohybrids. The PL spectrum of ZnFe 2 O 4 displayed the near band-edge emission at 529 nm, which was clearly associated with the basic defect density in the lattice structure ( Kumar et al. 2021 ). This band was also correlated to the weak green emission due to the presence of oxygen vacancy in spinel ferrite. In case of 5% PPy/ZnFe nanohybrid, two photoluminescence emission peaks at 435 nm and 411 nm were observed in addition to the characteristic peak at 529 nm, which were attributed to PPy and therefore confirmed the presence of PPy in ZnFe ( Rahman et al. 2023 ). 4.5 XPS studies The X-ray photoelectron spectroscopy (XPS) analysis results are provided in Fig. 5 (a-f). The overview of the XPS spectrum of pure ZnFe and PPy/ZnFe, Fig. 5 (a), revealed the existence of Zn, Fe, O, in ZnFe and Zn, Fe, O C, N in the PPy/ZnFe naohybrid. Fig. The high-resolution spectrum of Zn in PPy/ZnFe, Fig. 5 (b), showed peaks centered at 1045 eV and 1025 eV eV correlated to the existence of Zn 2p 1/2 and Zn 2p 3/2 and the + 2 oxidation state. The high resolution spectrum of Fe in PPy/ZnFe ,Fig. 5 (c), showed the peaks of Fe 2p at 724 eV and 711 eV attributed to Fe 2p 1/2 and Fe 2p 3/2 and the oxidation state of + 3 was confirmed for Fe. Thus, the existence of ZnFe 2 O 4 was established in PPy/ZnFe. The high resolution O1s spectrum ,Fig. 5 (d), revealed peaks at 531 eV and 529 eV which were assigned to the lattice oxygen binding with Zn and Fe (denoted as Zn–O and Fe–O)(Han et al. 2014 ). The high resolution spectrum of C1s of PPy/ZnFe ,Fig. 5 (e), shows peak at 284 eV attributed to the C = C chemical state and at 287 eV due to C = N/ C = O. The high resolution spectrum of N1s ,Fig. 5 (f), revealed satellite peaks at 398 eV, 400 eV and 401 eV ascribed to C = N, C–N and N-O respectively(Feng et al. 2020 ). The presence of the peaks related to Zn, Fe, C, O and N confirmed the structure of PPy/ZnFe nanohybrid. 4.6 UV analysis and calculation of bandgap The UV-visible spectra of ZnFe and PPy/ZnFe are given in Fig. 6 (a-d). The optical band gap of ZnFe 2 O 4 and PPy/ZnFe 2 O 4 nanohybrids were calculated using Kubelka-Munk equation ( Ghazkoob et al. 2021 ). The band gap for ZnFe was found to be 2.03 eV, Fig. 6 (a) ( Ghazkoob et al. 2021 ). The band gap values were found to be 1.94 eV for 1% PPy/ZnFe, Fig. 6 (b) ,1.66 eV for 3% PPy/ZnFe, Fig. 6 (c) and 1.38 eV for 5% PPy/ZnFe, Fig. 6 (d). With an increase in PPy content, ZnFe’s band gap consistently diminished, making it appropriate for utilization as a visible light photocatalyst. The BET surface area of ZnFe was observed to be 150 m 2 /gm and that of 1%PPy/ZnFe was close to 158 m 2 /g. The BET surface areas of 3% PPy/ZnFe and 5% PPy/ZnFe were observed to be 163 and 165 m 2 /g. The highest pore size and volume was noticed to be for 5% PPy/ZnFe, Table S1 . 4.7 Photocatalytic studies: effect of drug concentration CTZ-HCl was degraded using visible light-driven photocatalysis performed for a period of 60 minutes under visible light, and the UV spetrum revealed a pronounced peak at 229 nm(Souri et al. 2013 ). Figures 7 (a-d) reveal the reduction in the CTZ-HCl peak using ZnFe and its nanohybrids with PPy. In order to investigate the effects of CTZ-HCl concentration on the degradation behavior, solutions of 30 ppm, 50 ppm, and 70 ppm were taken in along with 50 mg of catalyst (given in supporting information as Figure S1 (a-d)). In case of ZnFe, for 30 ppm CTZ-HCl solution, almost 67% degradation was observed for 30 ppm, 59% for 50 ppm and 53% for 70 ppm. The rate constant (k) values for 30 ppm, 50 ppm, and 70 ppm were computed to be as 0.018 min − 1 , 0.015 min − 1 and 0.013 min − 1 respectively (given in supporting information as Figure S1 (a-d) inset). For 1% PPy/ZnFe, 30 ppm solution showed 71% degradation, 50 ppm showed 64% and 70 ppm showed 58% of degradation. The k values were found to be 0.020 cm − 1 for 30 ppm, 0.017 cm − 1 for 50 ppm and 0.015 cm − 1 for 70 ppm solution. The 3% PPy/ZnFe nanohybrid, showed 75% degradation for 30 ppm solution and almost 69% degradation was observed for 50 ppm solution, while 62% degradation was achieved in case of 70 ppm solution. The k values were found to be 0.023 min − 1 for 30 ppm, 0.020 min − 1 for 50 ppm and 0.017 min − 1 for 70 ppm solution respectively. Likewise, for 5% PPy/ZnFe, 82% degradation was observed 30 ppm, 74% for 50 ppm and 68% for 70 ppm. The k values were observed to be 0.029 min − 1 , 0.022 min − 1 , 0.019 min − 1 for 30 ppm, 50 ppm and 70 ppm respectively. The k values confirmed that the degradation followed the pseudo-first order model. To investigate the influence of catalyst concentration, 50 mg, 100 mg, and 150 mg of ZnFe and PPy/ZnFe nanohybrids were used to degrade a 70 ppm cetirizine dihydrochloride solution, as (shown in supooting information as Figure S2(a-d)). For ZnFe, 53%, 69%, 72% degradation was observed for 50 mg, 100 mg and 150 mg respectively. The k values were found to be 0.013 min − 1 , 0.020 min − 1 and 0.022 min − 1 respectively. The 1% PPy/ZnFe revealed 58% degradation for 50 mg catalyst, 74% for 100 mg and 86% for 150 mg. The k values were computed to be 0.015 min − 1 , 0.023 min − 1 and 0.033 min − 1 for 50 mg, 100 mg and 150 mg respectively. Similarly, 3% PPy/ZnFe, showed 62% for 50 mg, 79% for 100 mg and 91% for 150 mg. The observed k values are 0.017 min − 1 for 50 mg, 0.026 min − 1 for 100 mg and 0.040 min − 1 for 150 mg catalyst. Likewise, 5% PPy/ZnFe, exihibited 68% degradation for 50 mg, 86% for 100 mg and 98% for 150 mg in the same irradiation time. The k values were recorded as 0.019 min − 1 for 50 mg, 0.034 min − 1 and 0.066 min − 1 for 100 mg and 150 mg respectively. With the increase in concentration of catalyst, the degradation efficiency was found to increase very promptly. The kinetics of photocatalyst concentration also followedthe pesudo-first order kinetics model. 4.8 Radical scavenging experiments and TOC analysis To further understand the mechanism behind the enhanced photocatalytic performance of ZnFe and PPy/ZnFe nanohybrids, radical trapping studies were carried out to confirm the main reactive oxidative species involved in the photocatalytic degradation of the CTZ-HCl. Before being exposed to visible irradiation, CTZ-HCl solution was mixed with various scavengers, p-benzoquinone (PBQ) (O 2 ●− scavenger), ethylene diamine tetra acetic acid (EDTA) (h + scavenger), and isopropyl alcohol (IPA), which is an ● OH scavenger, Fig. 8 (a-d). Using ZnFe as photocatalyst, Fig. 8 (a) the degradation efficiency was reduced to 60% in presence of EDTA, 49% in presence of PBQ and 31% in presence of IPA. For 1% PPy/ZnFe, Fig. 8 (b), the degradation efficiency was reduced to 69%, 56%, and 40% in presence of EDTA, PBQ and IPA respectively. In case of 3% PPy/ZnFe, Fig. 8 (c), the reduction was seen up to 74% in presence of EDTA, 60% in presence of PBQ and 45% in presence of IPA. Similarly, in case of 5% PPy/ZnFe, Fig. 8 (d), degradation efficiency was reduced to 79% in presence of EDTA, 64% in presence of PBQ and 48% in presence of IPA. From radical trapping studies it was concluded that ● OH radicals were the main species involved in photocatalytic degradation of CTZ-HCl. The changes of total organic carbon (TOC) during photocatalytic degradation of CTZ-HCl in the presence of 5% PPy/ZnFe is shown in Fig. 9 . The gradual decrease of TOC represented the gradual disappearance of organic carbon and the reduce rate of TOC was estimated to be 98.32% after visible light irradiation for 60 min. It was illustrated that CTZ-HCl was converted to organic carbon. The degraded fragments were also analyzed by LCMS studies as given in supporting information, Figure S3. Since ● OH radicals were responsible for degradation as confirmed by radical scavenging studies, the degradation pathway proceeds by fragmenting the parent molecule (P1) into {4-[(4-chlorophenyl) (phenyl)methyl] piperazin-1-yl} acetaldehyde (M1) with m/z ratio as 325 that undergoes further fragmentation in presence of ● OH radicals to produce 4-[(4-chlorophenyl)(phenyl)methyl]piperazin-1-ol (M2, m/z 305) and N -[(4-chlorophenyl)methyl]- N - (hydroxymethyl)formamide (M3,m/z 199), Scheme 1 . The major degraded fragment as per LCMS profile is N -hydroxy- N -(2-oxoethyl) formamide (M5) with m/z value of 100. 4.9 Mechanism of degradation The photocatalytic mechanism of the PPy/ZnFe is presented in Scheme 2 . The photogenerated electrons in the CB of ZnFe are transferred to the highest occupied molecular orbital (HOMO) of PPy, where they recombine with the photogenerated holes. At the same time, the photogenerated electrons in the LUMO of PPy are separated and migrate to the surface to react with surface-adsorbed O 2 in order to generate O 2 −● radicals, and the photogenerated holes in the VB of ZnFe are also transferred to the surface for the photocatalytic evolution of ● OH radicals which are responsible for the photodegradation of CTZ-HCl. The synergistic interaction between the 2 components improves the photoinduced charge separation and suppress charge recombination, resulting in an enhanced photocatalytic performance. Moreover, photoinduced electrons are easily transferred in the nanohybrid due to the π-π stacking of in PPY, which leads to prevention in charge, resulting in significantly enhanced photocatalytic activity of the nanohybrid as compared to pristine ZnFe. ZnFe 2 O 4 and 5% PPy/ZnFe 2 O 4 showed remarkable photocatalytic activity even after 5cycles, which confirmed their extraordinary reusability. The Cetirizine hydrochloride was degraded to 62%, Fig. 10 (a), and 90.6% Fig. 10 (b), even after 5 cycles of using ZnFe 2 O 4 and 5% PPy/ZnFe 2 O 4 as catalyst. The 5%7 PPy/ZnFe 2 O 4 showed more stability than ZnFe 2 O 4 . The comparative studies provided in Table 1 reveal that the synthesized PPy/ZnFe nanohybrids are superior in terms of rapid degradation of CTZ-HCl within 60 min. Upon comparing degradation studies by other authors, we observed, Uheida et al . ( Uheida et al. 2019 ) reported 99% degradation of (5ppm) cetirizine under visible light in time span of 50 minutes utilizing PAN-CNT/TiO 2 -NH 2 . Mohamed et al . ( Mohamed et al. 2018 ) have reported 99% degradation for 50 ppm of cetirizine by PAN-MWCNT/TiO 2 –NH 2 in 40 min under UV light, while as Iqbal et al .(Iqbal et al. 2021 ) reported 87% degradation by 3D-ZVF in 120 minutes for 10 ppm of cetirizine. Talwar et al. ( Talwar et al. 2019 ) carried out heterogeneous photocatalytic degradation of cetirizine utilizing TiO 2 as photocatalyst and reported 98% degradation for 15 ppm of cetirizine in 420 min exposure time. Qureshi et al. ( Qureshi et al. 2019 ) performed UV light-assisted photocatalytic degradation of cetirizine using GO-ZnWO 4 as photocatalyst for 120 minutes and reported 89% degradation for the concentration of 10 ppm. In this study we have reported 98% of visible light induced degradation of 70 ppm cetirizine in a short time span of 60 minutes utilizing 150 mg of 5% PPy/ZnFe 2 O 4 . Our results are therefore comparable as well as superior to the ones reported by other authors who have used lower concentrations of cetirizine for degradation and also in terms of higher degradation efficiency attained in a short span of 60 minutes. Table 1 Comparative Studies demonstrating degradation of CTZ-HCl using different catalysts Catalyst Used Mechanism Involved Concentration of CTZ-HCl Degradation Time Degradation (%) PAN-CNT/TiO 2 -NH 2 (Uheida et al. 2019 ) Visible light Photocatalysis 5 mg/L 50 min 99% PAN-MWCNT/TiO 2 –NH 2 (Mohamed et al. 2018 ) UV-light photocatalysis (5–50 mg/L) 40 min 99% 3D-ZVF (Iqbal et al. 2021 ) UV-light Photocatalysis 10 mg/L 120 min 87% TiO 2 (Talwar et al. 2019 ) Heterogeneous Photocatalysis 15 ppm 420 min 98% GO-ZnWO 4 (Qureshi et al. 2019 ) UV irradiation photocatalysis 10 mg/L 120 min 89% 5. Conclusion ZnFe and nanohybrids PPy/ZnFe were investigated for their photocatalytic activity against CTZ-HCl under visible light irradiation. The structural characterization of the PPy/ZnFe nanohybrids was confirmed via FTIR, UV-visible, XRD, XPS and SEM studies. The UV results showed a considerable reduction in band gap upon increasing the loading of PPy in ZnFe. The XRD analysis, confirmed transformation of crystalline ZnFe to semi-crystalline nature. The photocatalytic performance was evaluated by photodegradation of CTZ-HCl under an exposure time of 60 min. Maximum degradation 98% was shown by 5% PPy/ZnFe and was highest among all the catalysts. The kinetics followed first-order model. The results from recyclability tests revealed that the photo catalysts maybe safely used for five cycles. LCMS showed formation of fragments of molar mas as low as 100 and a tentative degradation pathway was proposed. Declarations Acknowledgement Dr. Ufana Riaz wishes to acknowledge National Science Foundation (Award # 2122044), the NSF PREM for Hybrid Nanoscale Systems between NCCU and Penn State for providing financial assistance. Authors’ contributions Shaista Gaffar synthesized the polymers and carried out the characterization section. Prof. Elham Aazam contributed towards interpretation while Dr. Ufana Riaz conceived the entire experimental work and 506 carried out the interpretation of all the experimental data. Data availability Provided in manuscript and supplementary information Compliance with ethical standards Ethical approval Not applicable Consent to participate The authors have consent to participate. Consent to publish The authors have consent to publish. Competing interests The authors declare that they have no competing interests. Funding information Not applicable References Algarni TS, Al-Mohaimeed AM, Al-Odayni A-B, Abduh NAY (2022) Activated Carbon/ZnFe2O4 Nanocomposite Adsorbent for Efficient Removal of Crystal Violet Cationic Dye from Aqueous Solutions. Nanomaterials 12:3224. https://doi.org/10.3390/nano12183224 Ashraf A, Munir R, Albasher G et al (2023) Utilization of ZnFe 2 O 4 -Polyaniline (PANI), ZnFe 2 O 4 -Polystyrene (PST), and ZnFe 2 O 4 -Polypyrrole (PPy) nanocomposites for removal of Red X-GRL and Direct Sky Blue dyes from wastewater: Equilibrium, kinetic and thermodynamic studies. J Environ Sci Heal Part A 58:914–934. https://doi.org/10.1080/10934529.2023.2263323 Boumaza S, Boudjemaa A, Bouguelia A et al (2010) Visible light induced hydrogen evolution on new hetero-system ZnFe2O4/SrTiO3. Appl Energy 87:2230–2236. https://doi.org/10.1016/j.apenergy.2009.12.016 Chamani S, Sadeghi E, Peighambardoust NS et al (2022) Photocatalytic hydrogen evolution performance of metal ferrites /polypyrrole nanocomposites. Int J Hydrogen Energy 47:32940–32954. https://doi.org/10.1016/j.ijhydene.2022.07.193 Das KK, Patnaik S, Mansingh S et al (2020) Enhanced photocatalytic activities of polypyrrole sensitized zinc ferrite/graphitic carbon nitride n-n heterojunction towards ciprofloxacin degradation, hydrogen evolution and antibacterial studies. J Colloid Interface Sci 561:551–567. https://doi.org/10.1016/j.jcis.2019.11.030 Dippong T (2021) Characterization and Applications of Metal Ferrite Nanocomposites. Nanomaterials 12:107. https://doi.org/10.3390/nano12010107 Ethiraj AS, Uttam P, K V, et al (2020) Photocatalytic performance of a novel semiconductor nanocatalyst: Copper doped nickel oxide for phenol degradation. Mater Chem Phys 242:122520. https://doi.org/10.1016/j.matchemphys.2019.122520 Feng M, Lu W, Zhou Y et al (2020) Synthesis of polypyrrole/nitrogen-doped porous carbon matrix composite as the electrode material for supercapacitors. Sci Rep 10:15370. https://doi.org/10.1038/s41598-020-72392-x Gaffar S, Kumar A, Alam J, Riaz U (2023a) Efficient visible light–induced photocatalytic degradation of tetracycline hydrochloride using CuFe2O4 and PANI/CuFe2O4 nanohybrids. Environ Sci Pollut Res 30:108878–108888. https://doi.org/10.1007/s11356-023-29976-7 Gaffar S, Kumar A, Riaz U (2023b) Synthesis techniques and advance applications of spinel ferrites: A short review. J Electroceram. https://doi.org/10.1007/s10832-023-00333-x Gaffar S, Mir A, Kumar A et al (2023c) Microwave-assisted rapid catalytic degradation of isoniazid drug using polythiophene/ZnFe2O4 organic-inorganic hybrids. J Mol Liq 390:123112. https://doi.org/10.1016/j.molliq.2023.123112 Ghazkoob N, Zargar Shoushtari M, Kazeminezhad I, Lari Baghal SM (2021) Structural, magnetic and optical investigation of AC pulse electrodeposited zinc ferrite nanowires with different diameters and lengths. J Magn Magn Mater 537:168113. https://doi.org/10.1016/j.jmmm.2021.168113 Han L, Zhou X, Wan L et al (2014) Synthesis of ZnFe2O4 nanoplates by succinic acid-assisted hydrothermal route and their photocatalytic degradation of rhodamine B under visible light. J Environ Chem Eng 2:123–130. https://doi.org/10.1016/j.jece.2013.11.031 Iqbal M, Ahmad MZ, Qureshi K et al (2021) Template free zinc vanadate flower synthesis, characterization and efficiency for cetirizine-dihydrochloride degradation under UV light irradiation. Mater Chem Phys 272:124968. https://doi.org/10.1016/j.matchemphys.2021.124968 Jeseentharani V, George M, Jeyaraj B et al (2013) Synthesis of metal ferrite (MFe 2 O 4, M = Co, Cu, Mg, Ni, Zn) nanoparticles as humidity sensor materials. J Exp Nanosci 8:358–370. https://doi.org/10.1080/17458080.2012.690893 Kashyap J, Gautam S, Ashraf SM, Riaz U (2018) Synergistic Performance of Sonolytically Synthesized Poly(1-naphthylamine)/TiO 2 Nanohybrids: Degradation Studies of Amido Black‐10B Dye. ChemistrySelect 3:11926–11934. https://doi.org/10.1002/slct.201802688 Kumar V, Kumar N, Bhushan Das S et al (2021) Sol-gel assisted synthesis and tuning of structural, photoluminescence, magnetic and multiferroic properties by annealing temperature in nanostructured zinc ferrite. Mater Today Proc 47:6242–6248. https://doi.org/10.1016/j.matpr.2021.05.215 Makofane A, Motaung DE, Hintsho-Mbita NC (2021) Photocatalytic degradation of methylene blue and sulfisoxazole from water using biosynthesized zinc ferrite nanoparticles. Ceram Int 47:22615–22626. https://doi.org/10.1016/j.ceramint.2021.04.274 Mar-Ortiz AF, Salazar-Rábago JJ, Sánchez-Polo M et al (2020) Photodegradation of antihistamine chlorpheniramine using a novel iron-incorporated carbon material and solar radiation. Environ Sci Water Res Technol 6:2607–2618. https://doi.org/10.1039/D0EW00413H Mohamed A, Salama A, Nasser WS, Uheida A (2018) Photodegradation of Ibuprofen, Cetirizine, and Naproxen by PAN-MWCNT/TiO2–NH2 nanofiber membrane under UV light irradiation. Environ Sci Eur 30:47. https://doi.org/10.1186/s12302-018-0177-6 Oliva J, Sanchez J, Servin SR et al (2020) Enhancing the photocatalytic degradation of ciprofloxacin contaminant using a combined laser irradiation (285/365 nm) and porous g-C3N4. Mater Chem Phys 252:123198. https://doi.org/10.1016/j.matchemphys.2020.123198 Petrie B, Barden R, Kasprzyk-Hordern B (2015) A review on emerging contaminants in wastewaters and the environment: Current knowledge, understudied areas and recommendations for future monitoring. Water Res 72:3–27. https://doi.org/10.1016/j.watres.2014.08.053 Qureshi K, Ahmad MZ, Bhatti IA et al (2019) Graphene oxide decorated ZnWO4 architecture synthesis, characterization and photocatalytic activity evaluation. J Mol Liq 285:778–789. https://doi.org/10.1016/j.molliq.2019.04.139 Rahman S, Rahman Khan MM, Deb B et al (2023) Effective and simple fabrication of pyrrole and thiophene-based poly(Py-co-Th)/ZnO composites for high photocatalytic performance. South Afr J Chem Eng 43:303–311. https://doi.org/10.1016/j.sajce.2022.11.010 Sato T, Haneda K, Seki M, Iijima T (1990) Morphology and magnetic properties of ultrafine ZnFe2O4 particles. Appl Phys Solids Surf 50:13–16. https://doi.org/10.1007/BF00323947 Souri E, Hatami A, Shabani Ravari N et al (2013) Validating a stability indicating HPLC method for kinetic study of cetirizine degradation in acidic and oxidative conditions. Iran J Pharm Res IJPR 12:287–294 Stricker M (1988) [Community prevention in Switzerland–what next? A round table discussion]. Soz Praventivmed 33:106–108. https://doi.org/10.1007/BF02098313 Sutar RS, Rathod VK (2015) Ultrasound assisted enzyme catalyzed degradation of Cetirizine dihydrochloride. Ultrason Sonochem 24:80–86. https://doi.org/10.1016/j.ultsonch.2014.10.016 Szkoda M, Trzciński K, Nowak AP et al (2020) The effect of morphology and crystalline structure of Mo/MoO3 layers on photocatalytic degradation of water organic pollutants. Mater Chem Phys 248:122908. https://doi.org/10.1016/j.matchemphys.2020.122908 Talwar S, Chaudhary P, Sangal VK, Verma A (2019) Study of Degradation of Pharmaceutical Drug Cetirizine Using TiO2 Photocatalysis. pp 303–310 Uheida A, Mohamed A, Belaqziz M, Nasser WS (2019) Photocatalytic degradation of Ibuprofen, Naproxen, and Cetirizine using PAN-MWCNT nanofibers crosslinked TiO2-NH2 nanoparticles under visible light irradiation. Sep Purif Technol 212:110–118. https://doi.org/10.1016/j.seppur.2018.11.030 Yuan X, Pei F, Luo X et al (2021) Fabrication of ZnO/Au@Cu2O heterojunction towards deeply oxidative photodegradation of organic dyes. Sep Purif Technol 262:118301. https://doi.org/10.1016/j.seppur.2021.118301 Zhu B, Cheng F, Zhong W et al (2022) Mechanistic Insight into Degradation of Cetirizine under UV/Chlorine Treatment: Experimental and Quantum Chemical Studies. Water 14:1323. https://doi.org/10.3390/w14091323 Zia J, Ajeer M, Riaz U (2019) Visible–light driven photocatalytic degradation of bisphenol-A using ultrasonically synthesized polypyrrole/K-birnessite nanohybrids: Experimental and DFT studies. J Environ Sci 79:161–173. https://doi.org/10.1016/j.jes.2018.11.021 Zia J, Farhat SM, Aazam ES, Riaz U (2021) Highly efficient degradation of metronidazole drug using CaFe2O4/PNA nanohybrids as metal-organic catalysts under microwave irradiation. Environ Sci Pollut Res 28:4125–4135. https://doi.org/10.1007/s11356-020-10694-3 Zia J, Riaz U (2020) Studies on the spectral, morphological and magnetic properties of PCz-PPy copolymer encapsulated BaFe2O4 nanohybrids. J Mater Sci Mater Electron 31:22856–22865. https://doi.org/10.1007/s10854-020-04812-7 Zia J, Riyazuddin M, Aazam ES, Riaz U (2020) Rapid catalytic degradation of amoxicillin drug using ZnFe2O4/PCz nanohybrids under microwave irradiation. Mater Sci Eng B 261:114713. https://doi.org/10.1016/j.mseb.2020.114713 Schemes Schemes 1 and 2 are available in the Supplementary Files section Supplementary Files Scheme1.png Scheme 1 Tentative degradation pathway of CTZ-HCl Scheme2.png Scheme 2 Proposed mechanism of degradation of PPy/ZnFe under visible light irradiation. SupportingInformationESPR.docx Cite Share Download PDF Status: Published Journal Publication published 01 Nov, 2024 Read the published version in Environmental Science and Pollution Research → Version 1 posted Reviewers agreed at journal 29 Mar, 2024 Reviewers invited by journal 29 Mar, 2024 Editor invited by journal 29 Feb, 2024 Editor assigned by journal 21 Feb, 2024 First submitted to journal 14 Feb, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3955347","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":285508755,"identity":"69ecff5a-e84a-4d12-8346-8753b15d97e7","order_by":0,"name":"shayista Gaffar","email":"","orcid":"","institution":"Jamia Millia Islamia","correspondingAuthor":false,"prefix":"","firstName":"shayista","middleName":"","lastName":"Gaffar","suffix":""},{"id":285508756,"identity":"799debd1-d36f-45dc-8106-14f717cb7f1c","order_by":1,"name":"elham S Aazam","email":"","orcid":"","institution":"King Abdulaziz University","correspondingAuthor":false,"prefix":"","firstName":"elham","middleName":"S","lastName":"Aazam","suffix":""},{"id":285508757,"identity":"0fa1173f-1894-47e2-b09e-7c3e9c94f3ed","order_by":2,"name":"ufana riaz","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA8ElEQVRIiWNgGAWjYDAC5gNAokKCh5+9gYEZJngArxa2BCBxxkZOsucAKVoY29KMDW4kILTgBQbHmJ89+MF2OLHh5hvDzwUVNgz87Q2MhwvwamEzN+zhOZzYODvHWHrGmTQGiTMHGA7PwKflfoOZBI/E4cRm6RwDad62wwwGEgkMh3nw2sL+TfKPweHENskzxr+J1MJjJs2TkGbMIwFkEKVF8hhPmbTMARs5CZ60MmueM2k8EmcONuDVwneMfZvk238SPPbHD2++zVNhI8ff3nz4Mz4tSIDDAEQCFTM2EKeBgYH9AbEqR8EoGAWjYIQBAHL5SiRENw6mAAAAAElFTkSuQmCC","orcid":"","institution":"jamia millia islamia","correspondingAuthor":true,"prefix":"","firstName":"ufana","middleName":"","lastName":"riaz","suffix":""}],"badges":[],"createdAt":"2024-02-14 05:49:28","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3955347/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3955347/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s11356-024-35467-0","type":"published","date":"2024-11-01T16:12:54+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":54037552,"identity":"166cf0eb-ff5a-46c1-9716-a9bc4df0e182","added_by":"auto","created_at":"2024-04-03 17:11:38","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":1149431,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSEM of (a) ZnFe, (b) 1% PPy/ZnFe, (c) 3% PPy/ ZnFe, (d) 5% PPy/ ZnFe.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/0706c6cd51b0ff65f017d6f2.png"},{"id":54037564,"identity":"dba16ad5-f96c-4443-ad79-d287ff8162b5","added_by":"auto","created_at":"2024-04-03 17:11:41","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":333236,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eIR spectra of (a) ZnFe,(b) 1% PPy/ZnFe ,(c) 3% PPy/ZnFe,(d) 5% PPy/ZnFe nanohybrids\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/c3c84fc73ff3b1c146082b54.png"},{"id":54037554,"identity":"9ddde381-a7c1-4cf1-ab1d-f07799276b55","added_by":"auto","created_at":"2024-04-03 17:11:39","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":399172,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eXRD profile of ZnFe and PPy/ZnFe nanohybrids\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/fa62c536ffc5e96c86267bbb.png"},{"id":54037567,"identity":"496734ce-437e-40fb-99dd-3760762ca684","added_by":"auto","created_at":"2024-04-03 17:11:42","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":274529,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePL spectra of ZnFe and 5% PPy/ZnFe nanohybrid.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/ac13a188b56c4a92e6aff63b.png"},{"id":54037559,"identity":"810a7e5f-459c-4041-99ce-5f0694a0f6bc","added_by":"auto","created_at":"2024-04-03 17:11:40","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":479689,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a) overview of XPS profile of ZnFe and PPy/ZnFe (b) high resolution Zn 2p ,(c) high resolution Fe 2p ,(d) high resolution O 1s, (e) high resolution C 1s,(f) high resolution N 1s\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/fc52445f05d528daf92fbece.png"},{"id":54037557,"identity":"d9be88a1-46d2-4d9d-bdb3-313b190a377c","added_by":"auto","created_at":"2024-04-03 17:11:40","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":225151,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDiffuse reflectance spectra and Kubelka-Munk plot (inset) of (a) ZnFe (b) 1% PPy/ZnFe, (c) 3% PPy/ZnFe, (d) 5% PPy/ZnFe\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/778eb54bbb1f641450b0bd49.png"},{"id":54037570,"identity":"85d2bab1-2e87-473e-9185-6f13cb2768de","added_by":"auto","created_at":"2024-04-03 17:11:43","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":379783,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eUV plots of CTZ-HCl degradation using (a) ZnFe, (b) 1% PPy-ZnFe, (c) 3% PPy-ZnFe, (d) 5% PPy-ZnFe as photo catalysts.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/f86f19a3f0cb0973a1cb1a1b.png"},{"id":54037569,"identity":"26a33d82-e0cb-4f00-b6be-1648e7f0a21b","added_by":"auto","created_at":"2024-04-03 17:11:42","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":425389,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eEffect of addition of radical scavenger on (a) ZnFe, (b) 1% PPy-ZnFe, (c) 3% PPy-ZnFe, (d) 5% PPy-ZnFe.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/f0b6e0b808d4469e7089fab5.png"},{"id":54037563,"identity":"9dbad818-9bf1-4dd3-93a9-5602b33df257","added_by":"auto","created_at":"2024-04-03 17:11:41","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":96611,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAnalysis of total organic carbon (TOC) during photocatalytic degradation of CTZ-HCl using 5% PPy/ZnFe as photocatalyst under visible light irradiation.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/a741678bad719a38fde2eda0.png"},{"id":54037566,"identity":"a7f8d787-fa4d-463d-b3f6-e21e8c452259","added_by":"auto","created_at":"2024-04-03 17:11:41","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":138368,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eRecyclability test using (a) ZnFe, (b) 5% PPy/ZnFe.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/9ae1acf25025804172ec7a09.png"},{"id":68206398,"identity":"ab8a803b-416c-42d8-be00-440743ddbf9f","added_by":"auto","created_at":"2024-11-04 16:32:07","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4523900,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/36a92a38-d2d2-46b9-964c-c0d563747fca.pdf"},{"id":54037565,"identity":"160559cf-04bf-4b4e-820a-4d59ff893d0e","added_by":"auto","created_at":"2024-04-03 17:11:41","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":158332,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1 Tentative degradation pathway of CTZ-HCl\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"Scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/370a118c88959e251b11f267.png"},{"id":54037560,"identity":"9f966f54-9e71-4c60-bbbf-d0ad2c8adf93","added_by":"auto","created_at":"2024-04-03 17:11:40","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":128567,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 2 Proposed mechanism of degradation of PPy/ZnFe under visible light irradiation.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"Scheme2.png","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/39eae4ac2e14f982efd8cc58.png"},{"id":54037553,"identity":"6ccaf0d2-2891-4e2d-9c5c-6778cd14cddc","added_by":"auto","created_at":"2024-04-03 17:11:39","extension":"docx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":984988,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingInformationESPR.docx","url":"https://assets-eu.researchsquare.com/files/rs-3955347/v1/d2e73d280efe5a6a01516b90.docx"}],"financialInterests":"","formattedTitle":"Visible light Induced Photocatalytic Activity of Polypyrrole Decorated Zinc Ferrite Green Nanohybrids Against Cetirizine Hydrochloride Degradation","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe release of pollutants into water bodies has increased during the past few decades as a result of the rapid development of contemporary society \u003cb\u003e(\u003c/b\u003eMar-Ortiz et al. \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Numerous pollutants are found in waste water from industries, medical facilities, and households. These pollutants pass through aquatic environments and have a negative impact on aquatic life \u003cb\u003e(\u003c/b\u003eSzkoda et al. \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2020\u003c/span\u003e,Oliva et al. \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Pesticides, dyes, and medications are among the contaminants that are of the utmost significance \u003cb\u003e(\u003c/b\u003eEthiraj et al. \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2020\u003c/span\u003e,Yuan et al. \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). The discharge of pharmaceutical products in ground water, surface water, and drinking water leads to accumulation of antibiotics, anti-inflammatory drugs, psychiatric drugs, analgesics, and antihistamines. A report from the united nations has estimated that 1500 km\u003csup\u003e3\u003c/sup\u003e of wastewater are produced annually, of which over 70% is discharged into freshwater sources untreated, contributing to the serious problem of water pollution \u003cb\u003e(\u003c/b\u003eStricker \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e1988\u003c/span\u003e,Souri et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2013\u003c/span\u003e) .\u003c/p\u003e \u003cp\u003eCetirizine hydrochloride is a drug from the antihistamine category that is found in numerous water sources. 2-(2-(4-(4-chlorophenyl) phenyl methyl) piperazin-1-yl) ethoxy) acetic acid di hydrochloride is the chemical name for cetirizine hydrochloride \u003cb\u003e(\u003c/b\u003eZhu et al. \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). It is a second-generation antihistamine belonging to the piperazine category that is employed for treating urticaria, allergic rhinitis, edoema, and allergies. In many parts of the world, cetirizine hydrochloride (CTZ-HCl) is now recognized as a significant contaminant \u003cb\u003e(\u003c/b\u003ePetrie et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2015\u003c/span\u003e, Sutar and Rathod \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2015\u003c/span\u003e\u003cb\u003e)\u003c/b\u003e. In reaction to repeated or prolonged exposure to CTZ-HCl at greater concentrations, numerous harmful cumulative consequences have been observed \u003cb\u003e(\u003c/b\u003eMohamed et al. \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Few experiments have been conducted to remove this contaminant from water sources \u003cb\u003e(\u003c/b\u003eSouri et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2013\u003c/span\u003e, Zhu et al. \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Among the physical and chemical techniques utilized for water remediation, photo-catalytic degradation offers a number of advantages due to its potential effectiveness in degrading the contaminants under light irradiation without causing secondary pollution \u003cb\u003e(\u003c/b\u003eGaffar et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2023a\u003c/span\u003e, Gaffar et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2023c\u003c/span\u003e, Zia et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2020\u003c/span\u003e,Zia et al. \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2021\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eMetal ferrites (MFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e) are ferromagnetic materials that have been used in a variety of applications because of their unique magnetic, optical, and electrical characteristics \u003cb\u003e(\u003c/b\u003eDippong \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2021\u003c/span\u003e,Gaffar et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2023b\u003c/span\u003e,Makofane et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). These substances have found widespread use as catalysts, medication delivery systems, pigments, sensors, fluids, magnetic recording, and other functions \u003cb\u003e(\u003c/b\u003eChamani et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2022\u003c/span\u003e,Jeseentharani et al. \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). One of the most extensively researched ferrites for photocatalytic and photo electro catalytic uses is zinc ferrite, or ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e \u003cb\u003e(\u003c/b\u003eSato et al. \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e1990\u003c/span\u003e, Boumaza et al. \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). Conducting polymers (CPs) are known as sensitizers which play a vital role in the reduction of band gap of various metal oxides(Zia and Riaz \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2020\u003c/span\u003e)(Kashyap et al. \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2018\u003c/span\u003e)(Zia et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). \u003cem\u003eDas et al\u003c/em\u003e. (Das et al. \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2020\u003c/span\u003e) have studied the photocatalytic activities of polypyrrole sensitized zinc ferrite/graphitic carbon nitride n-n Heterojunction towards Ciprofloxacin Degradation (92%). \u003cem\u003eAshraf et al\u003c/em\u003e. \u003cb\u003e(\u003c/b\u003eAshraf et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2023\u003c/span\u003e) utilized the polypyrrole/ zinc ferrite nanocomposites for the removal of Red X-GRL and direct sky-blue dyes from waste-water. However, no work has been done on degradation of CTZ-HCl by zinc Ferrites. In our recent work, we have investigated the microwave-assisted rapid catalytic degradation of isoniazid drug using polythiophene/ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e organic-inorganic hybrids \u003cb\u003e(\u003c/b\u003eGaffar et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2023c\u003c/span\u003e). The degradation mechanism was proposed to be the generation of hotspots under microwave irradiation. The microwave technique does not consider the band gap of the ferrites. Hence in this study, we have explored the ban dgap variation of ZnFe upon interaction with PPy and its photocatalytic activity under visible light irradiation. The synthesized nano materials were characterized for their spectral, thermal, and morphological properties. Based on radical scavenging experiments and LCMS studies, the mechanism of degradation was hypothesized.\u003c/p\u003e"},{"header":"2. Materials and Methods","content":"\u003cp\u003eZinc chloride (ZnCl\u003csub\u003e2\u003c/sub\u003e), (136.286 g/mol, \u0026ge;\u0026thinsp;99.995% trace metals basis, Merck, India), ferric chloride hexahydrate (FeCl\u003csub\u003e3\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO) (270.294 g/mol, \u0026ge;\u0026thinsp;98.995% trace metals basis Sigma-Aldrich, USA), pyrrole (C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003eN) (67.09 g/mol, 98%, Loba Chemie Pvt. Ltd, India), ammonium hydroxide solution ( 28% NH\u003csub\u003e3\u003c/sub\u003e in H\u003csub\u003e2\u003c/sub\u003eO, \u0026ge;\u0026thinsp;99.99% trace metals basis, Sigma Aldrich ,USA) ethylene diamine tetra acetic acid (EDTA) (HO\u003csub\u003e2\u003c/sub\u003eCCH\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003eNCH\u003csub\u003e2\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eN(CH\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003eH), (372.24 g/mol, Merck, India), benzoquinone (C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e) (108.09 g/mol Merck, India), isopropyl alcohol (C\u003csub\u003e3\u003c/sub\u003eH\u003csub\u003e8\u003c/sub\u003eO) (\u0026ge;\u0026thinsp;99.7%, Merck, India), methanol (\u0026ge;\u0026thinsp;99.6%, Sigma-Aldrich, USA), ethanol (\u0026ge;\u0026thinsp;99.7% Merck, India) and distilled water were used without further purification. Cetirizine hydrochloride (C\u003csub\u003e21\u003c/sub\u003eH\u003csub\u003e25\u003c/sub\u003eClN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u0026middot;2HCl) (molecular weight 461.8 g/mol) was obtained from Sigma Aldrich.\u003c/p\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Synthesis of PPy/ZnFe nanohybrids\u003c/h2\u003e \u003cp\u003eZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (ZnF) nanoparticles were synthesized as per method reported in our earlier studies\u003cb\u003e(\u003c/b\u003eGaffar et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2023c\u003c/span\u003e). The synthesized ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and pyrrole monomer were added together in a 150 ml conical flask containing 60 ml methanol: water mixture (30 ml v/v) and the mixture was sonicated at 25\u0026deg;C on ultrasonic bath (30 kHz) for 30 min. Ferric chloride dissolved in 30 ml was added to the above reaction mixture monomer oxidant ratio (1:1) and was then exposed to further sonication for about 4 h. The synthesized nanohybrids were filtered and washed several times with distilled water and dried in vacuum oven for 24h at 80\u0026deg;C. On the basis of the weight ratios of the ferrite/monomer used, the nanohybrids were designated as 1% PPy/ZnFe, 3% PPy/ZnFe and 5% PPy/ZnFe.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Characterization","content":"\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Spectral Analysis\u003c/h2\u003e \u003cp\u003eShimadzu IR Affinity-1 FT-IR spectrophotometer was used to capture the FT-IR spectra of ZnFe and PPy/ZnFe nanohybrids. In the form of KBr pellets, spectra with frequencies in the range of 400 to 4000 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were captured. Diffuse reflectance spectroscopy (Perkin-Elmer Lamda-30) was used to measure the UV-Vis reflectance spectra of synthetic materials. The wave length ranged from 200 to 800 nm.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Morphological Analysis\u003c/h2\u003e \u003cp\u003eOn a Philips Pw-3710 X-ray diffractometer using Ni-filtered Cu-K radiation, the X-ray diffraction patterns of ZnFe and PPy/ZnFe nanohybrids were obtained. Field emission-scanning electron microscopy (FE-SEM) was used to analyze the morphology (Leo Supra 50 V P, Carl Zeiss, Germany).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.3 BET studies\u003c/h2\u003e \u003cp\u003eThe BET (Brunauer\u0026ndash;Emmett\u0026ndash;Teller) -specific surface area was calculated at P/P0\u0026thinsp;=\u0026thinsp;0.05\u0026ndash;0.25, and the pore size distribution and volume were derived from the adsorption branch by using the Barrett\u0026ndash;Joyner\u0026ndash;Halenda (BJH) mode.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.4 Photoluminescence studies\u003c/h2\u003e \u003cp\u003eRoom-temperature photoluminescence (PL) measurements were carried out with excitation by a 325 nm line of a He\u0026ndash;Cd laser to evaluate the optical property of ZnFe and its nanohybrid with PPy.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.5 Photocatalytic Activity\u003c/h2\u003e \u003cp\u003ePhotocatalytic activities were carried out in the presence of visible light by breaking down CTZ-HCl using a 500-watt halogen lamp. Approximately 150 mg of catalyst was dispersed in 300 ml of CTZ-HCl solution and the adsorption-desorption equilibrium between the CTZ-HCl solution and the catalyst was established by keeping it under dark condition for 3 hours. The solution was then exposed to visible light irradiation for 60 minutes, and at regular intervals of 0, 10, 20, 30, 40, 50, and 60 minutes, aliquots of the solution (5 ml) were taken from the solution and centrifuged. The UV spectra of the CTZ-HCl were captured using a Perkin-Elmer Lambda 30 type UV-Vis spectrophotometer. Cetirizine hydrochloride's λ\u003csub\u003emax\u003c/sub\u003e values were measured at a wavelength of 229 nm.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.6 Scavenging Experiments and Recyclability tests\u003c/h2\u003e \u003cp\u003eWe were able to investigate the reactive species that were responsible for the degradation process by using 5mM concentrations of the scavengers isopropyl alcohol (IPA) for the detection of \u003csup\u003e●\u003c/sup\u003eOH radicals, ethylene diamine tetra acetate (EDTA) for the detection of holes (h\u003csup\u003e+\u003c/sup\u003e), and benzoquinone for the detection of electrons (e\u003csup\u003e\u0026minus;\u003c/sup\u003e) \u003cb\u003e(\u003c/b\u003eGaffar et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2023a\u003c/span\u003e,Gaffar et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2023c\u003c/span\u003e). They were gradually introduced to the catalyst-containing cetirizine hydrochloride solution to observe how scavengers affected the rate of degradation. The recyclability of ZnFe and 5% PPy/ZnFe nanohybrids were demonstrated in the photocatalytic degradation procedure up to five cycles. ZnFe and 5% PPy/ZnFe were collected at the end of every cycle. The collected samples were washed with distilled water and dried in vacuum oven for about 6 h at 80\u003csup\u003eo\u003c/sup\u003eC.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.7 Analysis of degraded fragments\u003c/h2\u003e \u003cp\u003eFor detection and identification of degradation products, liquid chromatography-mass spectroscopy (LC-MS) was conducted using a Finnigan LCQ ion trap mass spectrometer equipped with an electro spray ionization interface (ESI) source and operated in 10 negative polarity mode fitted with a Genesis, C-18 column (4.6\u0026times;250mm) containing 4 \u0026micro;m packed particles (Alltech, Deerfield, Germany).The gradient HPLC separation was coupled with LC/MSD trap 6310, ion trap mass spectrometer (Agilent technologies). The experiments were carried out in triplicate for evaluating the effect of nanohybrid catalyst dosage and initial dye concentration in the degradation of MG. Mineralization of the dye was determined by measuring the total organic content (TOC) of the degraded dye at 10\u0026ndash;60 minutes on Shimadzu TOC-5000A total organic carbon analyzer.\u003c/p\u003e \u003c/div\u003e"},{"header":"4. Results and Discussion","content":"\u003cdiv id=\"Sec13\" class=\"Section2\"\u003e\n \u003ch2\u003e4.1 SEM analysis\u003c/h2\u003e\n \u003cp\u003eThe morphology of obtained ZnFe and PPy/ZnFe nanohybrids has been analyzed using SEM analysis displayed in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e (a-d). The SEM of ZnFe revealed intense bright, flower-like morphology with rough surface \u003cstrong\u003e(\u003c/strong\u003eRahman et al. \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). The SEM of 1% PPy/ZnFe and 3% PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e(b),(c) showed the formation of heterogeneous morphology with globular spherical aggregates of dark particles associated with PPy embedded with bright nodular particles which were correlated to ZnFe. The size of dark PPy particles was small but the distribution of the dark particles increased with the increasing in PPy confirming that the hybrid was heterogeneous and revealed mixed morphology. The SEM micrograph of 5% PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e(d), showed the formation of huge spherical clusters of dark and bright particles. The morphology clearly shows that huge structural transformation occurs upon increase of loading of PPy.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec14\" class=\"Section2\"\u003e\n \u003ch2\u003e4.2 IR analysis\u003c/h2\u003e\n \u003cp\u003eThe FTIR spectra of as synthesized ZnFe and PPy/ZnFe nanohybrids are shown in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e(a-d). The broad band absorption peak at 3415 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e in ZnFe ,Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e(a) was due to the presence of OH group of entrapped water. The peak at 1684 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was attrivutred to the metal-OH (M-OH) stretching vibration. Zn-O vibration was indicated by the presence of the peak at 846 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The peak at 657 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was attributed to Fe-O vibration, and represent the tetrahedral and octahedral modes of Fe in ZnFe. The existence of the peaks above supported the formation of ZnFe \u003cstrong\u003e(\u003c/strong\u003eGaffar et al. \u003cspan class=\"CitationRef\"\u003e2023c\u003c/span\u003e,Zia et al. \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e). In case of 1% PPy/ZnFe nanohybrid, Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e(b), the peak at 3309 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponded to the NH and OH stretching vibration of PPy and entrapped water respectively. The peaks at 1556 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1408 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were attributed to the C\u0026thinsp;=\u0026thinsp;N bands of pyrrole. The peak at 1197 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponded to N- C bending vibration of PPy.\u003c/p\u003e\n \u003cp\u003eThe peaks at 1043 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was attributed to C-H stretching vibration of PPy, while the peak associated with pyrrole ring appeared at 927 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The IR spectrum of 3% PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e(c), showed characteristic peak at 3148 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e representing \u0026ndash;OH and NH stretching vibration peaks. The peaks at 1546 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1402 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponds to C\u0026thinsp;=\u0026thinsp;N bands of pyrrole ring vibrations and the peak at 1192 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was observed representing N-C bending vibration. The peaks at 1045 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 921 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were also observed corresponding to =\u0026thinsp;C-H in plane vibration and N-H in plane vibrations of pyrrole ring. Similarly, the IR spectrum of 5% PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e(d), was also recorded displaying the characteristic peak at 3142 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e representing the \u0026ndash;OH stretching of H\u003csub\u003e2\u003c/sub\u003eO and NH of pyrrole. The peaks at 1550 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 1402 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1195 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were seen corresponding to C\u0026thinsp;=\u0026thinsp;C bands, N-H stretching vibration of pyrrole ring and N-C stretch vibration respectively. The peak at 1045 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e represented\u0026thinsp;=\u0026thinsp;C-H in plane vibration. The peak at 923 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was also observed corresponding to N-H in plane vibrations (Zia and Riaz \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e\u003cstrong\u003e)\u003c/strong\u003e. The region of NH/OH stretching vibration appeared to be broad and intense confirming the interaction of NH of pyrrole with the M-OH of ZnFe. The presence of the peaks associated with ZnFe and with PPy therefore confirmed the formation of the nanohybrid.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec15\" class=\"Section2\"\u003e\n \u003ch2\u003e4.3 XRD analysis\u003c/h2\u003eThe XRD profile of ZnFe and PPy/ZnFe nanohybrids are depicted in Figure 3. The XRD profile of ZnFe demonstrated peaks at 2\u0026theta;= 27.46\u0026deg;, 31.7\u0026deg;, 45.3\u0026deg;,56.3\u0026deg; and 74.9\u0026deg; which correspond to (220), (311), (400), (422), (511), and (533) crystal planes respectively. The cubic spinel structure precisely corresponded to all of the peaks described by JCPD card no. 01‐077‐ 0011\u003cstrong\u003e(Algarni et al. 2022)\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;.\u003c/strong\u003e\u003cbr\u003eThe 1% PPy/ZnFe nanohybrid revealed diffraction peaks at 2\u0026theta;= 18.06\u0026deg;, 31.5\u0026deg;, 35.08\u0026deg;, 56.46\u0026deg; and 61.7\u0026deg; corresponding to crystal planes (200), (220), (311), (511) and (533) respectively. For 3% PPy/ZnFe demonstrated crystal planes (200), (220), (311), (511) and (533) revealed by diffraction peaks at 2\u0026theta; =18.06\u0026deg;, 31.5\u0026deg;, 35.08\u0026deg;, 56.46\u0026deg; and 61.7\u0026deg; respectively. The nanohybrid 5% PPy/ZnFe revealed peaks at 2\u0026theta;\u0026thinsp;=\u0026thinsp;12.62\u0026deg;, 18.34\u0026deg;, 31.5\u0026deg;, 35.22\u0026deg;, 56.46\u0026deg; and 61.9\u0026deg; corresponding to crystal planes (001), (200), (220), (311), (511) and (533) respectively.\u003cp\u003eThe peaks that were previously seen in pure ZnFe and which correlate to different crystal planes have been retained in the nanohybrids 1% PPy/ZnFe, 3% PPy/ZnFe, and 5% PPy/ZnFe. The peak intensities of ZnFe were found to show broadening when PPy loading was increased from 1\u0026ndash;5%, confirming that the nanohybrid transformed into a semi-crystalline state. The structural changes appeared presumably due to the encapsulation by PPy chains that tend to arrange themselves along the ZnFe planes causing the later to be semi-crystalline.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec16\" class=\"Section2\"\u003e\n \u003ch2\u003e4.4 Photoluminescence studies\u003c/h2\u003e\n \u003cp\u003eThe Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e displays the room temperature PL spectrum of ZnFe and 5% PPy/ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanohybrids. The PL spectrum of ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e displayed the near band-edge emission at 529 nm, which was clearly associated with the basic defect density in the lattice structure\u003cstrong\u003e(\u003c/strong\u003eKumar et al. \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e). This band was also correlated to the weak green emission due to the presence of oxygen vacancy in spinel ferrite. In case of 5% PPy/ZnFe nanohybrid, two photoluminescence emission peaks at 435 nm and 411 nm were observed in addition to the characteristic peak at 529 nm, which were attributed to PPy and therefore confirmed the presence of PPy in ZnFe \u003cstrong\u003e(\u003c/strong\u003eRahman et al. \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e).\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec17\" class=\"Section2\"\u003e\n \u003ch2\u003e4.5 XPS studies\u003c/h2\u003e\n \u003cp\u003eThe X-ray photoelectron spectroscopy (XPS) analysis results are provided in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e (a-f). The overview of the XPS spectrum of pure ZnFe and PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e(a), revealed the existence of Zn, Fe, O, in ZnFe and Zn, Fe, O C, N in the PPy/ZnFe naohybrid. Fig. The high-resolution spectrum of Zn in PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e(b), showed peaks centered at 1045 eV and 1025 eV eV correlated to the existence of Zn 2p\u003csub\u003e1/2\u003c/sub\u003e and Zn 2p\u003csub\u003e3/2\u003c/sub\u003e and the +\u0026thinsp;2 oxidation state. The high resolution spectrum of Fe in PPy/ZnFe ,Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e(c), showed the peaks of Fe 2p at 724 eV and 711 eV attributed to Fe 2p\u003csub\u003e1/2\u003c/sub\u003e and Fe 2p\u003csub\u003e3/2\u003c/sub\u003e and the oxidation state of +\u0026thinsp;3 was confirmed for Fe. Thus, the existence of ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e was established in PPy/ZnFe. The high resolution O1s spectrum ,Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e(d), revealed peaks at 531 eV and 529 eV which were assigned to the lattice oxygen binding with Zn and Fe (denoted as Zn\u0026ndash;O and Fe\u0026ndash;O)(Han et al. \u003cspan class=\"CitationRef\"\u003e2014\u003c/span\u003e). The high resolution spectrum of C1s of PPy/ZnFe ,Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e(e), shows peak at 284 eV attributed to the C\u0026thinsp;=\u0026thinsp;C chemical state and at 287 eV due to C\u0026thinsp;=\u0026thinsp;N/ C\u0026thinsp;=\u0026thinsp;O. The high resolution spectrum of N1s ,Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e(f), revealed satellite peaks at 398 eV, 400 eV and 401 eV ascribed to C\u0026thinsp;=\u0026thinsp;N, C\u0026ndash;N and N-O respectively(Feng et al. \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e). The presence of the peaks related to Zn, Fe, C, O and N confirmed the structure of PPy/ZnFe nanohybrid.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec18\" class=\"Section2\"\u003e\n \u003ch2\u003e4.6 UV analysis and calculation of bandgap\u003c/h2\u003e\n \u003cp\u003eThe UV-visible spectra of ZnFe and PPy/ZnFe are given in Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e(a-d). The optical band gap of ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and PPy/ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanohybrids were calculated using Kubelka-Munk equation \u003cstrong\u003e(\u003c/strong\u003eGhazkoob et al. \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e). The band gap for ZnFe was found to be 2.03 eV, Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e(a) \u003cstrong\u003e(\u003c/strong\u003eGhazkoob et al. \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e). The band gap values were found to be 1.94 eV for 1% PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e(b) ,1.66 eV for 3% PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e(c) and 1.38 eV for 5% PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e(d). With an increase in PPy content, ZnFe\u0026rsquo;s band gap consistently diminished, making it appropriate for utilization as a visible light photocatalyst.\u003c/p\u003e\n \u003cp\u003eThe BET surface area of ZnFe was observed to be 150 m\u003csup\u003e2\u003c/sup\u003e/gm and that of 1%PPy/ZnFe was close to 158 m\u003csup\u003e2\u003c/sup\u003e/g. The BET surface areas of 3% PPy/ZnFe and 5% PPy/ZnFe were observed to be 163 and 165 m\u003csup\u003e2\u003c/sup\u003e/g. The highest pore size and volume was noticed to be for 5% PPy/ZnFe, Table \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec19\" class=\"Section2\"\u003e\n \u003ch2\u003e4.7 Photocatalytic studies: effect of drug concentration\u003c/h2\u003e\n \u003cp\u003eCTZ-HCl was degraded using visible light-driven photocatalysis performed for a period of 60 minutes under visible light, and the UV spetrum revealed a pronounced peak at 229 nm(Souri et al. \u003cspan class=\"CitationRef\"\u003e2013\u003c/span\u003e). Figures \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e(a-d) reveal the reduction in the CTZ-HCl peak using ZnFe and its nanohybrids with PPy. In order to investigate the effects of CTZ-HCl concentration on the degradation behavior, solutions of 30 ppm, 50 ppm, and 70 ppm were taken in along with 50 mg of catalyst (given in supporting information as Figure \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e(a-d)). In case of ZnFe, for 30 ppm CTZ-HCl solution, almost 67% degradation was observed for 30 ppm, 59% for 50 ppm and 53% for 70 ppm. The rate constant (k) values for 30 ppm, 50 ppm, and 70 ppm were computed to be as 0.018 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 0.015 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 0.013 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e respectively (given in supporting information as Figure \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e(a-d) inset). For 1% PPy/ZnFe, 30 ppm solution showed 71% degradation, 50 ppm showed 64% and 70 ppm showed 58% of degradation. The k values were found to be 0.020 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 30 ppm, 0.017 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 50 ppm and 0.015 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 70 ppm solution. The 3% PPy/ZnFe nanohybrid, showed 75% degradation for 30 ppm solution and almost 69% degradation was observed for 50 ppm solution, while 62% degradation was achieved in case of 70 ppm solution. The k values were found to be 0.023 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 30 ppm, 0.020 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 50 ppm and 0.017 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 70 ppm solution respectively. Likewise, for 5% PPy/ZnFe, 82% degradation was observed 30 ppm, 74% for 50 ppm and 68% for 70 ppm. The k values were observed to be 0.029 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 0.022 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 0.019 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 30 ppm, 50 ppm and 70 ppm respectively. The k values confirmed that the degradation followed the pseudo-first order model.\u003c/p\u003e\n \u003cp\u003eTo investigate the influence of catalyst concentration, 50 mg, 100 mg, and 150 mg of ZnFe and PPy/ZnFe nanohybrids were used to degrade a 70 ppm cetirizine dihydrochloride solution, as (shown in supooting information as Figure S2(a-d)). For ZnFe, 53%, 69%, 72% degradation was observed for 50 mg, 100 mg and 150 mg respectively. The k values were found to be 0.013 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 0.020 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 0.022 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e respectively. The 1% PPy/ZnFe revealed 58% degradation for 50 mg catalyst, 74% for 100 mg and 86% for 150 mg. The k values were computed to be 0.015 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 0.023 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 0.033 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 50 mg, 100 mg and 150 mg respectively. Similarly, 3% PPy/ZnFe, showed 62% for 50 mg, 79% for 100 mg and 91% for 150 mg. The observed k values are 0.017 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 50 mg, 0.026 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 100 mg and 0.040 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 150 mg catalyst. Likewise, 5% PPy/ZnFe, exihibited 68% degradation for 50 mg, 86% for 100 mg and 98% for 150 mg in the same irradiation time. The k values were recorded as 0.019 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 50 mg, 0.034 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 0.066 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 100 mg and 150 mg respectively. With the increase in concentration of catalyst, the degradation efficiency was found to increase very promptly. The kinetics of photocatalyst concentration also followedthe pesudo-first order kinetics model.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec20\" class=\"Section2\"\u003e\n \u003ch2\u003e4.8 Radical scavenging experiments and TOC analysis\u003c/h2\u003e\n \u003cp\u003eTo further understand the mechanism behind the enhanced photocatalytic performance of ZnFe and PPy/ZnFe nanohybrids, radical trapping studies were carried out to confirm the main reactive oxidative species involved in the photocatalytic degradation of the CTZ-HCl. Before being exposed to visible irradiation, CTZ-HCl solution was mixed with various scavengers, p-benzoquinone (PBQ) (O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e●\u0026minus;\u003c/sup\u003e scavenger), ethylene diamine tetra acetic acid (EDTA) (h\u003csup\u003e+\u003c/sup\u003e scavenger), and isopropyl alcohol (IPA), which is an \u003csup\u003e●\u003c/sup\u003eOH scavenger, Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e(a-d). Using ZnFe as photocatalyst, Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e(a) the degradation efficiency was reduced to 60% in presence of EDTA, 49% in presence of PBQ and 31% in presence of IPA. For 1% PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e(b), the degradation efficiency was reduced to 69%, 56%, and 40% in presence of EDTA, PBQ and IPA respectively.\u003c/p\u003e\n \u003cp\u003eIn case of 3% PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e(c), the reduction was seen up to 74% in presence of EDTA, 60% in presence of PBQ and 45% in presence of IPA. Similarly, in case of 5% PPy/ZnFe, Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e(d), degradation efficiency was reduced to 79% in presence of EDTA, 64% in presence of PBQ and 48% in presence of IPA. From radical trapping studies it was concluded that \u003csup\u003e●\u003c/sup\u003eOH radicals were the main species involved in photocatalytic degradation of CTZ-HCl. The changes of total organic carbon (TOC) during photocatalytic degradation of CTZ-HCl in the presence of 5% PPy/ZnFe is shown in Fig. \u003cspan class=\"InternalRef\"\u003e9\u003c/span\u003e.\u003c/p\u003e\n \u003cp\u003eThe gradual decrease of TOC represented the gradual disappearance of organic carbon and the reduce rate of TOC was estimated to be 98.32% after visible light irradiation for 60 min. It was illustrated that CTZ-HCl was converted to organic carbon. The degraded fragments were also analyzed by LCMS studies as given in supporting information, Figure S3. Since \u003csup\u003e●\u003c/sup\u003eOH radicals were responsible for degradation as confirmed by radical scavenging studies, the degradation pathway proceeds by fragmenting the parent molecule (P1) into {4-[(4-chlorophenyl) (phenyl)methyl] piperazin-1-yl} acetaldehyde (M1) with m/z ratio as 325 that undergoes further fragmentation in presence of \u003csup\u003e●\u003c/sup\u003eOH radicals to produce 4-[(4-chlorophenyl)(phenyl)methyl]piperazin-1-ol (M2, m/z 305) and \u003cem\u003eN\u003c/em\u003e-[(4-chlorophenyl)methyl]-\u003cem\u003eN\u003c/em\u003e- (hydroxymethyl)formamide (M3,m/z 199), Scheme \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e. The major degraded fragment as per LCMS profile is \u003cem\u003eN\u003c/em\u003e-hydroxy-\u003cem\u003eN\u003c/em\u003e-(2-oxoethyl) formamide (M5) with m/z value of 100.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec21\" class=\"Section2\"\u003e\n \u003ch2\u003e4.9 Mechanism of degradation\u003c/h2\u003e\n \u003cp\u003eThe photocatalytic mechanism of the PPy/ZnFe is presented in Scheme \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. The photogenerated electrons in the CB of ZnFe are transferred to the highest occupied molecular orbital (HOMO) of PPy, where they recombine with the photogenerated holes. At the same time, the photogenerated electrons in the LUMO of PPy are separated and migrate to the surface to react with surface-adsorbed O\u003csub\u003e2\u003c/sub\u003e in order to generate O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;●\u003c/sup\u003e radicals, and the photogenerated holes in the VB of ZnFe are also transferred to the surface for the photocatalytic evolution of \u003csup\u003e●\u003c/sup\u003eOH radicals which are responsible for the photodegradation of CTZ-HCl.\u003c/p\u003e\n \u003cp\u003eThe synergistic interaction between the 2 components improves the photoinduced charge separation and suppress charge recombination, resulting in an enhanced photocatalytic performance. Moreover, photoinduced electrons are easily transferred in the nanohybrid due to the \u0026pi;-\u0026pi; stacking of in PPY, which leads to prevention in charge, resulting in significantly enhanced photocatalytic activity of the nanohybrid as compared to pristine ZnFe.\u003c/p\u003e\n \u003cp\u003eZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and 5% PPy/ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e showed remarkable photocatalytic activity even after 5cycles, which confirmed their extraordinary reusability. The Cetirizine hydrochloride was degraded to 62%, Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e(a), and 90.6% Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e(b), even after 5 cycles of using ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and 5% PPy/ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e as catalyst. The 5%7 PPy/ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e showed more stability than ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e.\u003c/p\u003e\n \u003cp\u003eThe comparative studies provided in Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e reveal that the synthesized PPy/ZnFe nanohybrids are superior in terms of rapid degradation of CTZ-HCl within 60 min.\u003c/p\u003e\n \u003cp\u003eUpon comparing degradation studies by other authors, we observed, \u003cem\u003eUheida et al\u003c/em\u003e.\u003cstrong\u003e(\u003c/strong\u003eUheida et al. \u003cspan class=\"CitationRef\"\u003e2019\u003c/span\u003e) reported 99% degradation of (5ppm) cetirizine under visible light in time span of 50 minutes utilizing PAN-CNT/TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e. \u003cem\u003eMohamed et al\u003c/em\u003e. \u003cstrong\u003e(\u003c/strong\u003eMohamed et al. \u003cspan class=\"CitationRef\"\u003e2018\u003c/span\u003e) have reported 99% degradation for 50 ppm of cetirizine by PAN-MWCNT/TiO\u003csub\u003e2\u003c/sub\u003e \u0026ndash;NH\u003csub\u003e2\u003c/sub\u003e in 40 min under UV light, while as \u003cem\u003eIqbal et al\u003c/em\u003e.(Iqbal et al. \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e) reported 87% degradation by 3D-ZVF in 120 minutes for 10 ppm of cetirizine. \u003cem\u003eTalwar et al.\u003c/em\u003e \u003cstrong\u003e(\u003c/strong\u003eTalwar et al. \u003cspan class=\"CitationRef\"\u003e2019\u003c/span\u003e) carried out heterogeneous photocatalytic degradation of cetirizine utilizing TiO\u003csub\u003e2\u003c/sub\u003e as photocatalyst and reported 98% degradation for 15 ppm of cetirizine in 420 min exposure time. \u003cem\u003eQureshi et al.\u003c/em\u003e \u003cstrong\u003e(\u003c/strong\u003eQureshi et al. \u003cspan class=\"CitationRef\"\u003e2019\u003c/span\u003e) performed UV light-assisted photocatalytic degradation of cetirizine using GO-ZnWO\u003csub\u003e4\u003c/sub\u003e as photocatalyst for 120 minutes and reported 89% degradation for the concentration of 10 ppm. In this study we have reported 98% of visible light induced degradation of 70 ppm cetirizine in a short time span of 60 minutes utilizing 150 mg of 5% PPy/ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e. Our results are therefore comparable as well as superior to the ones reported by other authors who have used lower concentrations of cetirizine for degradation and also in terms of higher degradation efficiency attained in a short span of 60 minutes.\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\n \u003cdiv align=\"left\" class=\"colspec\"\u003e\u003cbr\u003e\u003c/div\u003e\u0026nbsp;\u003ctable id=\"Tab1\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eComparative Studies demonstrating degradation of CTZ-HCl using different catalysts\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ccolgroup cols=\"5\"\u003e\u003c/colgroup\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eCatalyst Used\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eMechanism Involved\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eConcentration of CTZ-HCl\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eDegradation Time\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eDegradation (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003ePAN-CNT/TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e (Uheida et al. \u003cspan class=\"CitationRef\"\u003e2019\u003c/span\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eVisible light Photocatalysis\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e5 mg/L\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50 min\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e99%\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003ePAN-MWCNT/TiO\u003csub\u003e2\u003c/sub\u003e\u0026ndash;NH\u003csub\u003e2\u003c/sub\u003e (Mohamed et al. \u003cspan class=\"CitationRef\"\u003e2018\u003c/span\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eUV-light photocatalysis\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e(5\u0026ndash;50 mg/L)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e40 min\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e99%\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3D-ZVF (Iqbal et al. \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eUV-light Photocatalysis\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10 mg/L\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e120 min\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e87%\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eTiO\u003csub\u003e2\u003c/sub\u003e (Talwar et al. \u003cspan class=\"CitationRef\"\u003e2019\u003c/span\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eHeterogeneous Photocatalysis\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15 ppm\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e420 min\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e98%\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eGO-ZnWO\u003csub\u003e4\u003c/sub\u003e (Qureshi et al. \u003cspan class=\"CitationRef\"\u003e2019\u003c/span\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eUV irradiation photocatalysis\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10 mg/L\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e120 min\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e89%\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n\u003c/div\u003e"},{"header":"5. Conclusion","content":"\u003cp\u003eZnFe and nanohybrids PPy/ZnFe were investigated for their photocatalytic activity against CTZ-HCl under visible light irradiation. The structural characterization of the PPy/ZnFe nanohybrids was confirmed via FTIR, UV-visible, XRD, XPS and SEM studies. The UV results showed a considerable reduction in band gap upon increasing the loading of PPy in ZnFe. The XRD analysis, confirmed transformation of crystalline ZnFe to semi-crystalline nature. The photocatalytic performance was evaluated by photodegradation of CTZ-HCl under an exposure time of 60 min. Maximum degradation 98% was shown by 5% PPy/ZnFe and was highest among all the catalysts. The kinetics followed first-order model. The results from recyclability tests revealed that the photo catalysts maybe safely used for five cycles. LCMS showed formation of fragments of molar mas as low as 100 and a tentative degradation pathway was proposed.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgement\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eDr. Ufana Riaz wishes to acknowledge National Science Foundation (Award # 2122044), the NSF PREM for Hybrid Nanoscale Systems between NCCU and Penn State for providing financial assistance.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors\u0026rsquo; contributions\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eShaista Gaffar synthesized the polymers and carried out the characterization section. Prof. Elham Aazam contributed towards interpretation while Dr. Ufana Riaz conceived the entire experimental work and 506 carried out the interpretation of all the experimental data.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003cstrong\u003eData availability\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;Provided in manuscript and supplementary information\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompliance with ethical standards\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;Ethical approval Not applicable\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003cstrong\u003eConsent to participate\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors have consent to participate.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003cstrong\u003eConsent to publish\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;The authors have consent to publish.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;The authors declare that they have no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding information\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;Not applicable\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eAlgarni TS, Al-Mohaimeed AM, Al-Odayni A-B, Abduh NAY (2022) Activated Carbon/ZnFe2O4 Nanocomposite Adsorbent for Efficient Removal of Crystal Violet Cationic Dye from Aqueous Solutions. Nanomaterials 12:3224. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/nano12183224\u003c/span\u003e\u003cspan address=\"10.3390/nano12183224\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAshraf A, Munir R, Albasher G et al (2023) Utilization of ZnFe 2 O 4 -Polyaniline (PANI), ZnFe 2 O 4 -Polystyrene (PST), and ZnFe 2 O 4 -Polypyrrole (PPy) nanocomposites for removal of Red X-GRL and Direct Sky Blue dyes from wastewater: Equilibrium, kinetic and thermodynamic studies. J Environ Sci Heal Part A 58:914\u0026ndash;934. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1080/10934529.2023.2263323\u003c/span\u003e\u003cspan address=\"10.1080/10934529.2023.2263323\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBoumaza S, Boudjemaa A, Bouguelia A et al (2010) Visible light induced hydrogen evolution on new hetero-system ZnFe2O4/SrTiO3. Appl Energy 87:2230\u0026ndash;2236. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.apenergy.2009.12.016\u003c/span\u003e\u003cspan address=\"10.1016/j.apenergy.2009.12.016\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eChamani S, Sadeghi E, Peighambardoust NS et al (2022) Photocatalytic hydrogen evolution performance of metal ferrites /polypyrrole nanocomposites. Int J Hydrogen Energy 47:32940\u0026ndash;32954. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.ijhydene.2022.07.193\u003c/span\u003e\u003cspan address=\"10.1016/j.ijhydene.2022.07.193\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDas KK, Patnaik S, Mansingh S et al (2020) Enhanced photocatalytic activities of polypyrrole sensitized zinc ferrite/graphitic carbon nitride n-n heterojunction towards ciprofloxacin degradation, hydrogen evolution and antibacterial studies. J Colloid Interface Sci 561:551\u0026ndash;567. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jcis.2019.11.030\u003c/span\u003e\u003cspan address=\"10.1016/j.jcis.2019.11.030\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDippong T (2021) Characterization and Applications of Metal Ferrite Nanocomposites. Nanomaterials 12:107. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/nano12010107\u003c/span\u003e\u003cspan address=\"10.3390/nano12010107\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eEthiraj AS, Uttam P, K V, et al (2020) Photocatalytic performance of a novel semiconductor nanocatalyst: Copper doped nickel oxide for phenol degradation. Mater Chem Phys 242:122520. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.matchemphys.2019.122520\u003c/span\u003e\u003cspan address=\"10.1016/j.matchemphys.2019.122520\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFeng M, Lu W, Zhou Y et al (2020) Synthesis of polypyrrole/nitrogen-doped porous carbon matrix composite as the electrode material for supercapacitors. Sci Rep 10:15370. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1038/s41598-020-72392-x\u003c/span\u003e\u003cspan address=\"10.1038/s41598-020-72392-x\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGaffar S, Kumar A, Alam J, Riaz U (2023a) Efficient visible light\u0026ndash;induced photocatalytic degradation of tetracycline hydrochloride using CuFe2O4 and PANI/CuFe2O4 nanohybrids. Environ Sci Pollut Res 30:108878\u0026ndash;108888. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s11356-023-29976-7\u003c/span\u003e\u003cspan address=\"10.1007/s11356-023-29976-7\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGaffar S, Kumar A, Riaz U (2023b) Synthesis techniques and advance applications of spinel ferrites: A short review. J Electroceram. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10832-023-00333-x\u003c/span\u003e\u003cspan address=\"10.1007/s10832-023-00333-x\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGaffar S, Mir A, Kumar A et al (2023c) Microwave-assisted rapid catalytic degradation of isoniazid drug using polythiophene/ZnFe2O4 organic-inorganic hybrids. J Mol Liq 390:123112. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.molliq.2023.123112\u003c/span\u003e\u003cspan address=\"10.1016/j.molliq.2023.123112\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGhazkoob N, Zargar Shoushtari M, Kazeminezhad I, Lari Baghal SM (2021) Structural, magnetic and optical investigation of AC pulse electrodeposited zinc ferrite nanowires with different diameters and lengths. J Magn Magn Mater 537:168113. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jmmm.2021.168113\u003c/span\u003e\u003cspan address=\"10.1016/j.jmmm.2021.168113\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHan L, Zhou X, Wan L et al (2014) Synthesis of ZnFe2O4 nanoplates by succinic acid-assisted hydrothermal route and their photocatalytic degradation of rhodamine B under visible light. J Environ Chem Eng 2:123\u0026ndash;130. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jece.2013.11.031\u003c/span\u003e\u003cspan address=\"10.1016/j.jece.2013.11.031\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eIqbal M, Ahmad MZ, Qureshi K et al (2021) Template free zinc vanadate flower synthesis, characterization and efficiency for cetirizine-dihydrochloride degradation under UV light irradiation. Mater Chem Phys 272:124968. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.matchemphys.2021.124968\u003c/span\u003e\u003cspan address=\"10.1016/j.matchemphys.2021.124968\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJeseentharani V, George M, Jeyaraj B et al (2013) Synthesis of metal ferrite (MFe 2 O 4, M = Co, Cu, Mg, Ni, Zn) nanoparticles as humidity sensor materials. J Exp Nanosci 8:358\u0026ndash;370. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1080/17458080.2012.690893\u003c/span\u003e\u003cspan address=\"10.1080/17458080.2012.690893\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKashyap J, Gautam S, Ashraf SM, Riaz U (2018) Synergistic Performance of Sonolytically Synthesized Poly(1-naphthylamine)/TiO 2 Nanohybrids: Degradation Studies of Amido Black‐10B Dye. ChemistrySelect 3:11926\u0026ndash;11934. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/slct.201802688\u003c/span\u003e\u003cspan address=\"10.1002/slct.201802688\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKumar V, Kumar N, Bhushan Das S et al (2021) Sol-gel assisted synthesis and tuning of structural, photoluminescence, magnetic and multiferroic properties by annealing temperature in nanostructured zinc ferrite. Mater Today Proc 47:6242\u0026ndash;6248. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.matpr.2021.05.215\u003c/span\u003e\u003cspan address=\"10.1016/j.matpr.2021.05.215\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMakofane A, Motaung DE, Hintsho-Mbita NC (2021) Photocatalytic degradation of methylene blue and sulfisoxazole from water using biosynthesized zinc ferrite nanoparticles. Ceram Int 47:22615\u0026ndash;22626. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.ceramint.2021.04.274\u003c/span\u003e\u003cspan address=\"10.1016/j.ceramint.2021.04.274\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMar-Ortiz AF, Salazar-R\u0026aacute;bago JJ, S\u0026aacute;nchez-Polo M et al (2020) Photodegradation of antihistamine chlorpheniramine using a novel iron-incorporated carbon material and solar radiation. Environ Sci Water Res Technol 6:2607\u0026ndash;2618. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/D0EW00413H\u003c/span\u003e\u003cspan address=\"10.1039/D0EW00413H\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMohamed A, Salama A, Nasser WS, Uheida A (2018) Photodegradation of Ibuprofen, Cetirizine, and Naproxen by PAN-MWCNT/TiO2\u0026ndash;NH2 nanofiber membrane under UV light irradiation. Environ Sci Eur 30:47. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1186/s12302-018-0177-6\u003c/span\u003e\u003cspan address=\"10.1186/s12302-018-0177-6\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eOliva J, Sanchez J, Servin SR et al (2020) Enhancing the photocatalytic degradation of ciprofloxacin contaminant using a combined laser irradiation (285/365 nm) and porous g-C3N4. Mater Chem Phys 252:123198. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.matchemphys.2020.123198\u003c/span\u003e\u003cspan address=\"10.1016/j.matchemphys.2020.123198\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePetrie B, Barden R, Kasprzyk-Hordern B (2015) A review on emerging contaminants in wastewaters and the environment: Current knowledge, understudied areas and recommendations for future monitoring. Water Res 72:3\u0026ndash;27. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.watres.2014.08.053\u003c/span\u003e\u003cspan address=\"10.1016/j.watres.2014.08.053\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQureshi K, Ahmad MZ, Bhatti IA et al (2019) Graphene oxide decorated ZnWO4 architecture synthesis, characterization and photocatalytic activity evaluation. J Mol Liq 285:778\u0026ndash;789. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.molliq.2019.04.139\u003c/span\u003e\u003cspan address=\"10.1016/j.molliq.2019.04.139\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRahman S, Rahman Khan MM, Deb B et al (2023) Effective and simple fabrication of pyrrole and thiophene-based poly(Py-co-Th)/ZnO composites for high photocatalytic performance. South Afr J Chem Eng 43:303\u0026ndash;311. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.sajce.2022.11.010\u003c/span\u003e\u003cspan address=\"10.1016/j.sajce.2022.11.010\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSato T, Haneda K, Seki M, Iijima T (1990) Morphology and magnetic properties of ultrafine ZnFe2O4 particles. Appl Phys Solids Surf 50:13\u0026ndash;16. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/BF00323947\u003c/span\u003e\u003cspan address=\"10.1007/BF00323947\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSouri E, Hatami A, Shabani Ravari N et al (2013) Validating a stability indicating HPLC method for kinetic study of cetirizine degradation in acidic and oxidative conditions. Iran J Pharm Res IJPR 12:287\u0026ndash;294\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eStricker M (1988) [Community prevention in Switzerland\u0026ndash;what next? A round table discussion]. Soz Praventivmed 33:106\u0026ndash;108. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/BF02098313\u003c/span\u003e\u003cspan address=\"10.1007/BF02098313\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSutar RS, Rathod VK (2015) Ultrasound assisted enzyme catalyzed degradation of Cetirizine dihydrochloride. Ultrason Sonochem 24:80\u0026ndash;86. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.ultsonch.2014.10.016\u003c/span\u003e\u003cspan address=\"10.1016/j.ultsonch.2014.10.016\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSzkoda M, Trzciński K, Nowak AP et al (2020) The effect of morphology and crystalline structure of Mo/MoO3 layers on photocatalytic degradation of water organic pollutants. Mater Chem Phys 248:122908. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.matchemphys.2020.122908\u003c/span\u003e\u003cspan address=\"10.1016/j.matchemphys.2020.122908\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTalwar S, Chaudhary P, Sangal VK, Verma A (2019) Study of Degradation of Pharmaceutical Drug Cetirizine Using TiO2 Photocatalysis. pp 303\u0026ndash;310\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eUheida A, Mohamed A, Belaqziz M, Nasser WS (2019) Photocatalytic degradation of Ibuprofen, Naproxen, and Cetirizine using PAN-MWCNT nanofibers crosslinked TiO2-NH2 nanoparticles under visible light irradiation. Sep Purif Technol 212:110\u0026ndash;118. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.seppur.2018.11.030\u003c/span\u003e\u003cspan address=\"10.1016/j.seppur.2018.11.030\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYuan X, Pei F, Luo X et al (2021) Fabrication of ZnO/Au@Cu2O heterojunction towards deeply oxidative photodegradation of organic dyes. Sep Purif Technol 262:118301. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.seppur.2021.118301\u003c/span\u003e\u003cspan address=\"10.1016/j.seppur.2021.118301\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhu B, Cheng F, Zhong W et al (2022) Mechanistic Insight into Degradation of Cetirizine under UV/Chlorine Treatment: Experimental and Quantum Chemical Studies. Water 14:1323. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/w14091323\u003c/span\u003e\u003cspan address=\"10.3390/w14091323\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZia J, Ajeer M, Riaz U (2019) Visible\u0026ndash;light driven photocatalytic degradation of bisphenol-A using ultrasonically synthesized polypyrrole/K-birnessite nanohybrids: Experimental and DFT studies. J Environ Sci 79:161\u0026ndash;173. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jes.2018.11.021\u003c/span\u003e\u003cspan address=\"10.1016/j.jes.2018.11.021\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZia J, Farhat SM, Aazam ES, Riaz U (2021) Highly efficient degradation of metronidazole drug using CaFe2O4/PNA nanohybrids as metal-organic catalysts under microwave irradiation. Environ Sci Pollut Res 28:4125\u0026ndash;4135. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s11356-020-10694-3\u003c/span\u003e\u003cspan address=\"10.1007/s11356-020-10694-3\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZia J, Riaz U (2020) Studies on the spectral, morphological and magnetic properties of PCz-PPy copolymer encapsulated BaFe2O4 nanohybrids. J Mater Sci Mater Electron 31:22856\u0026ndash;22865. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10854-020-04812-7\u003c/span\u003e\u003cspan address=\"10.1007/s10854-020-04812-7\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZia J, Riyazuddin M, Aazam ES, Riaz U (2020) Rapid catalytic degradation of amoxicillin drug using ZnFe2O4/PCz nanohybrids under microwave irradiation. Mater Sci Eng B 261:114713. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.mseb.2020.114713\u003c/span\u003e\u003cspan address=\"10.1016/j.mseb.2020.114713\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Schemes","content":"\u003cp\u003eSchemes 1 and 2 are available in the Supplementary Files section\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":true,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"environmental-science-and-pollution-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"espr","sideBox":"Learn more about [Environmental Science and Pollution Research](https://www.springer.com/journal/11356)","snPcode":"11356","submissionUrl":"https://submission.nature.com/new-submission/11356/3","title":"Environmental Science and Pollution Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"cetirizine hydrochloride, antihistamine, polypyrrole, photocatalysis","lastPublishedDoi":"10.21203/rs.3.rs-3955347/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3955347/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe present work reports photocatalytic degradation of cetirizine hydrochloride (CTZ-HCl) utilizing polypyrrole (PPy) nanohybrids with ZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (ZnFe) nanoparticles. The synthesized materials were characterized using UV-Visible spectroscopy, X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), Photoluminescence (PL) spectroscopy, BET and scanning electron microscopy (SEM) techniques. IR and XRD analysis confirmed the formation of ZnFe/PPy nanohybrids. UV reflectance studies revealed that the band gap was found to decrease with increase in the loading of PPy and Kubelka -Munk plots confirmed the bandgap values to be 2.03 eV for ZnFe, 1.94 eV for 1% PPy/ZnFe, 1.66 eV for 3% PPy/ZnFe and 1.38 eV for 5% PPy/ZnFe. The photocatalytic performance against CTZ-HCl degradation was performed under visible light irradiation for 60 min. The effect of catalyst dosage and the effect of drug concentration were investigated to confirm degradation behavior of the PPy/ZnFe photocatalysts. The degradation followed the pseudo first order kinetics model. Maximum photocatalytic degradation was observed to be 98% within 60 minutes using 5% PPy/ZnFe as the photocatalyst. The recyclability tests revealed that the 5% PPy/ZnFe photocatalyst was reusable up to 4 cycles. Radical scavenging studies confirmed the generation of \u003csup\u003e●\u003c/sup\u003eOH radicals that were responsible for the drug degradation. The degraded fragments were analyzed using LCMS technique and the tentative mechanism of degradation was proposed.\u003c/p\u003e","manuscriptTitle":"Visible light Induced Photocatalytic Activity of Polypyrrole Decorated Zinc Ferrite Green Nanohybrids Against Cetirizine Hydrochloride Degradation","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-04-03 17:11:11","doi":"10.21203/rs.3.rs-3955347/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2024-03-30T00:17:46+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-03-29T22:19:22+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"Environmental Science and Pollution Research","date":"2024-02-29T18:29:04+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-02-21T05:23:20+00:00","index":"","fulltext":""},{"type":"submitted","content":"Environmental Science and Pollution Research","date":"2024-02-14T19:56:27+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"environmental-science-and-pollution-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"espr","sideBox":"Learn more about [Environmental Science and Pollution Research](https://www.springer.com/journal/11356)","snPcode":"11356","submissionUrl":"https://submission.nature.com/new-submission/11356/3","title":"Environmental Science and Pollution Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"1ad3e526-98c2-4e14-8331-f3a3b2fc629f","owner":[],"postedDate":"April 3rd, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-11-04T16:21:34+00:00","versionOfRecord":{"articleIdentity":"rs-3955347","link":"https://doi.org/10.1007/s11356-024-35467-0","journal":{"identity":"environmental-science-and-pollution-research","isVorOnly":false,"title":"Environmental Science and Pollution Research"},"publishedOn":"2024-11-01 16:12:54","publishedOnDateReadable":"November 1st, 2024"},"versionCreatedAt":"2024-04-03 17:11:11","video":"","vorDoi":"10.1007/s11356-024-35467-0","vorDoiUrl":"https://doi.org/10.1007/s11356-024-35467-0","workflowStages":[]},"version":"v1","identity":"rs-3955347","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3955347","identity":"rs-3955347","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}