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

doi:10.21203/rs.3.rs-3955347/v1

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

https://doi.org/10.21203/rs.3.rs-3955347/v1

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published 01 Nov, 2024

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The present work reports photocatalytic degradation of cetirizine hydrochloride (CTZ-HCl) utilizing polypyrrole (PPy) nanohybrids with ZnFe₂O₄ (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

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 km³ 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 (MFe₂O₄) 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 ZnFe₂O₄ (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/ZnFe₂O₄ 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.

Zinc chloride (ZnCl₂), (136.286 g/mol, ≥ 99.995% trace metals basis, Merck, India), ferric chloride hexahydrate (FeCl₃·6H₂O) (270.294 g/mol, ≥ 98.995% trace metals basis Sigma-Aldrich, USA), pyrrole (C₄H₅N) (67.09 g/mol, 98%, Loba Chemie Pvt. Ltd, India), ammonium hydroxide solution ( 28% NH₃ in H₂O, ≥ 99.99% trace metals basis, Sigma Aldrich ,USA) ethylene diamine tetra acetic acid (EDTA) (HO₂CCH₂)₂NCH₂CH₂N(CH₂CO₂H), (372.24 g/mol, Merck, India), benzoquinone (C₆H₄O₂) (108.09 g/mol Merck, India), isopropyl alcohol (C₃H₈O) (≥ 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 (C₂₁H₂₅ClN₂O₃·2HCl) (molecular weight 461.8 g/mol) was obtained from Sigma Aldrich.

2.1 Synthesis of PPy/ZnFe nanohybrids

ZnFe₂O₄ (ZnF) nanoparticles were synthesized as per method reported in our earlier studies(Gaffar et al. 2023c). The synthesized ZnFe₂O₄ 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.

3.1 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^oC.

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.

4.1 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 H₂O 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/ZnFe₂O₄ nanohybrids. The PL spectrum of ZnFe₂O₄ 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 ZnFe₂O₄ 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 ZnFe₂O₄ and PPy/ZnFe₂O₄ 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 m²/gm and that of 1%PPy/ZnFe was close to 158 m²/g. The BET surface areas of 3% PPy/ZnFe and 5% PPy/ZnFe were observed to be 163 and 165 m²/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) (O₂^●− 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 O₂ in order to generate O₂^−● 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.

ZnFe₂O₄ and 5% PPy/ZnFe₂O₄ 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 ZnFe₂O₄ and 5% PPy/ZnFe₂O₄ as catalyst. The 5%7 PPy/ZnFe₂O₄ showed more stability than ZnFe₂O₄.

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/TiO₂-NH₂. Mohamed et al. (Mohamed et al. 2018) have reported 99% degradation for 50 ppm of cetirizine by PAN-MWCNT/TiO₂ –NH₂ 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 TiO₂ 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-ZnWO₄ 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/ZnFe₂O₄. 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/TiO₂-NH₂ (Uheida et al. 2019)	Visible light Photocatalysis	5 mg/L	50 min	99%
PAN-MWCNT/TiO₂–NH₂ (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%
TiO₂ (Talwar et al. 2019)	Heterogeneous Photocatalysis	15 ppm	420 min	98%
GO-ZnWO₄ (Qureshi et al. 2019)	UV irradiation photocatalysis	10 mg/L	120 min	89%

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.

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

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Competing interests

The authors declare that they have no competing interests.

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Schemes 1 and 2 are available in the Supplementary Files section

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

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

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Journal Publication

Version 1

Abstract

Figures

1. Introduction

2. Materials and Methods

2.1 Synthesis of PPy/ZnFe nanohybrids

3. Characterization

3.1 Spectral Analysis

3.2 Morphological Analysis

3.3 BET studies

3.4 Photoluminescence studies

3.5 Photocatalytic Activity

3.6 Scavenging Experiments and Recyclability tests

3.7 Analysis of degraded fragments

4. Results and Discussion

4.1 SEM analysis

4.2 IR analysis

4.3 XRD analysis

4.4 Photoluminescence studies

4.5 XPS studies

4.6 UV analysis and calculation of bandgap

4.7 Photocatalytic studies: effect of drug concentration

4.8 Radical scavenging experiments and TOC analysis

4.9 Mechanism of degradation

5. Conclusion

Declarations

References

Schemes

Supplementary Files

Status:

Journal Publication

Version 1