Elucidating Synergistic Effect of In-Situ Hybrid Process Towards Paraquat Abatement

Elucidating Synergistic Effect of In-Situ Hybrid Process Towards Paraquat Abatement | 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 Elucidating Synergistic Effect of In-Situ Hybrid Process Towards Paraquat Abatement Yamini Pandey, Aarsee Dhindsa, Anoop Verma, Amrit Pal Toor This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3909915/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Presence of non-biodegradable organic compounds, mainly pesticides in water bodies peril humans as well as aquatic life. Paraquat (PQ) is one such widely used Class II herbicide associated with Parkinson’s disease. Herein, pristine TiO 2 (PT), as well as metal (Fe-PT, Ni-PT) and nonmetal (C-PT, S-PT), modified TiO 2 was synthesized using hydrothermal treatment for mineralization and degradation of PQ. The crystallite size from XRD exhibited the prepared catalysts to be nanomaterials while FESEM confirmed the nanorod formation. Moreover, morphological analysis established the occurrence of doping in PT. Through optical properties, reduction in band gap from 3.2 eV to 2.4 eV was found which was accompanied by decrease in electron-hole recombination rate. Further, nanocomposites were investigated for PQ removal with S-PT depicting 93% degradation under solar radiations followed by Fe-PT degrading 87% PQ indicating that with optimum doping levels and proper reduction of band gap, TiO 2 can be made more enthusiastic towards degradation and remediation process. Further, hybrid process employing photocatalysis and photo-Fenton simultaneously was utilised by synthesising Fe-S-PT, a codoped catalyst. This codoped Fe-S-PT resulted in a sharp decrement of 47% in processing time which is attributed to the presence of OH˙ and e − . Moreover, a degradation mechanism for Fe-S-PT was proposed along with the evaluation of extent of mineralization taking place. Lately, intermediates formed during the process were identified. Overall, study is extremely significant towards providing a practical and economical solution for PQ degradation using hybrid process within 80 mins at the benign pH of 6.3. Photocatalysis Photo-Fenton Synergy Paraquat co-Doped TiO2 Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 Figure 16 1. Introduction With every passing day world is moving towards development however, this development comes at the cost of environment. Rapid growth of population along with urbanization and industrialization results in pollution ranging from air to water to soil with water pollution emerging as a major societal challenge accelerating at the same pace as that of industries and human society. Contamination of water bodies with chemicals is no longer a hidden truth with agricultural activities, pharmaceutical, cosmetics, tannery, and dyes being the major contributors (Marien et al., 2017 ). Amongst various effluents, pesticides/herbicides from agriculture practices act as the prominent contaminants. The property of these materials being toxic as well as non-biodegradable in nature makes the situation even worse. Paraquat (PQ) is one such extensively used herbicide leaving behind both health and environmental hazards. Its fast adsorption onto leaves, high solubility in water, recalcitrant nature along with resistance towards microbial degradation makes it a subject of concern (Florenci et al., 2004; Moctezuma et al., 1999 ). Therefore, it is required to carry out commercial management of pesticides keeping strict control over their application which in itself is a challenge as with the increase in population need for high-quality crops is increasing. So, the most promising alternative is to perform their degradation into simpler and non-toxic species which are safe for the environment. Pesticides can be degraded either by microbial action or by employing Advanced Oxidation Process (AOP). However, microbial action faces a major drawback i.e., it is a very slow process (Moctezuma et al., 1999 ) and pesticides like PQ are resistant to microbial degradation limiting their application towards depolluting wastewater. Contrary to this, AOP is a practical, powerful and impactful approach toward water remediation which is a sustainable cum greener technology (Kumar et al., 2018 ). Photocatalysis is a widely explored AOP technique characterized with production of highly reactive OH˙ which is unselective in nature and performs degradation at room temperature (Bianco et al., 2005; Cantavenera et al., 2007 ). Among variety of photocatalysts, TiO 2 is substantially explored owing to its characteristic features-low cost, high photosensitivity, non-toxic, and innocuous. However, single photocatalysis involving TiO 2 suffers major drawbacks-limited spectrum activation resulting in low quantum yield in visible region and rapid recombination of photocarriers, questioning its photocatalytic performance (Suwannaruang et al., 2018 ). As a result, formation of heterojunction comes to rescue which enhances separation efficiency of photocarriers along with photo response of the catalyst allowing to harvest freely available sunlight making the process sustainable, greener, and economical (Swain & Basu, 2021 ). Variety of literature discusses the positive effect of doping TiO 2 with metal or nonmetal towards the inhibition of organic pollutants from water (Damacena et al., 2023 ; Dong et al., 2011 ; El Mragui et al., 2021 ; Keerthana et al., 2022 ; Kundu et al., 2014 ; Nakhate et al., 2010 ; Shaban et al., 2019 ). Apart from photocatalysis, photo-Fenton is another type of AOP where Fe 2+ /Fe 3+ reacts with H 2 O 2 under highly acidic pH conditions for generation of OH˙ (Phan et al., 2023). But; unfortunately, AOP at commercial scale is still in limbo due to stumbling blocks like costly dopant synthesis, difficulty in catalyst separation, long treatment time, iron sludge formation, high dosage of H 2 O 2 , requirement of highly acidic conditions (Ncube et al., 2023 ; Talwar et al., 2019 ; Thakur & Örmeci, 2020 ). Hence, it is a challenge to replace traditional AOP with commercially viable and economical process. In the quest of monitoring PQ, emphasis has been on the role of pure or modified TiO 2 but majorly involves utilization of UV or visible light (Cantavenera et al., 2007 ; Eleburuike et al., 2016 ; Florêncio et al., 2004 ; Suwannaruang et al., 2018 ). Few works also investigated Fenton/Photo-Fenton process towards PQ removal however two major challenges i.e., high acidic environment and high H 2 O 2 dosage pertain (Oliveira et al., 2012 ; Santos et al., 2011 ; Trovó et al., 2013 ). Along with these drawbacks, another issue of high reaction time is consistent making the practical application of the process questionable (Cantavenera et al., 2007 ; Eleburuike et al., 2016 ; Marien et al., 2019 ; Santos et al., 2011 ). Moreover, research prominently lacks the knowledge of various active species responsible for PQ degradation which hinders getting exact knowledge of the mechanism followed by the catalysts. Considering all the above-discussed gaps, this study involves modification of electronic structure of TiO 2 intending to compare the effect of metal and non-metal incorporation towards PQ abatement under sunlight. Moreover, with primary focus on providing an industrially viable solution coping with all the drawbacks of the individual processes, an in-situ hybrid technique involving photocatalysis and photo-Fenton is carried out which to the best of our knowledge is first such study on PQ. Further investigations involve the study of structural and optical properties of samples along with mechanistic properties for determination of major active species. The extent of mineralization and kinetics of the model pollutant have also been discussed giving a clear insight into the mechanism followed for PQ removal along with various intermediates formed throughout the process. 2. Experimental Procedure 2.1 Materials PQ (98% pure) was acquired from Sigma Aldrich. Glacial acetic acid and sodium acetate used for making buffers was supplied by CDH. TiO 2 was purchased from Evonik India and 30% (v/v) H 2 O 2 from CDH. NaOH pellets, nickel nitrate heptahydrate, thiourea, graphite, and ferrous nitrate nona hydrate were supplied by Loba Chemie. Scavenger studies were performed using isopropyl alcohol (IPA) and sodium chloride acquired from CDH, silver nitrate supplied by Sigma Aldrich, and 1,4-p-benzoquinone (p-BQ) from TCI. Preparation for all solutions was done using distilled water. 2.2 Nanocomposite Synthesis PT and all other photocatalysts were synthesized hydrothermally with P25 TiO 2 as the precursor. PT synthesis involved dispersion of 2g P25 TiO 2 into 100 mL NaOH (10 M) followed by vigorous stirring and thus obtained homogenized solution was placed into a Teflon lined autoclave for hydrothermal treatment at 150˙C for 12 h. The precipitate was then cooled, filtered, and subjected to multiple washings with HCl (1M) and distilled water till neutral pH was attained. The obtained powder was then oven dried and calcined at 450˙C for 3 h. Similar procedure was followed for amalgamating Fe-PT, Ni-PT, S-PT, and C-PT by stirring the required amount of metal/nonmetal precursor and PT and then subjecting the mixture to hydrothermal treatment. The precursor for Fe, Ni, S, and C was ferrous nitrate nona hydrate, nickel nitrate heptahydrate, thiourea, and graphite powder respectively. Fe-S-PT synthesis involved the incorporation of Fe into the above prepared S-PT via hydrothermal process. 2.3 Protocol for Evaluating Degradation Activity Photocatalytic experiments involving UV irradiation were carried out in a UV chamber having 8 blue-black UV (365 nm) tubes on top of the chamber and magnetic stirrer at the bottom over which a hemispherical slurry reactor was placed. For performing reactions under sunlight, similar setup was used without any chamber. Moreover, for hybrid process under sunlight; the same setup was provided with air spargers and H 2 O 2 was added prior to the reaction. After every fixed time interval sample was collected, filtered using 0.22 µm microfilters, and then analyzed using UV-Vis spectrophotometer. 2.4 Instrumentation and Analytical Determinations 2.4.1 Catalyst Characterization In order to investigate the various phases of the synthesized photocatalysts, a powder X-ray Diffractometer (XRD) analyzer (Pan analytical X’Pert Pro diffractometer (D/max rA) at 45 kV and 40 mA with Cu (Kα = 1.504060 Ǻ) in the range of 2θ = 20°–90° was used. The Fourier transform infrared (FT-IR) spectrum of all the materials was measured in the range of 4000 − 600 cm − 1 using Spectrum RX-I. To analyze the structural morphology as well as the chemical composition of the catalysts, a field emission scanning electron microscope (FE-SEM) (Zeiss EV050) equipped with energy dispersive X-ray (EDX) (Bruker AXS, QuanTax 20) was used. The surface composition of the materials was acquired with X-ray Photoelectron Spectroscopy (XPS) on Physical Electronics-PHI 5000 VersaProbe III-ESCA system. The BET analysis of the surface area, pore volume, and pore size were studied using Quantachrome Autosorb 1 analyzer. The optical properties were further studied using multiple analytical techniques. The band gap energy of all the photocatalysts was compared using UV-DRS (Shimadzu UV–Vis spectrophotometer-UV 2400) with BaSO 4 as a reference. Further, the rate of electron-hole recombination was determined by photoluminescence (PL) spectra (Hitachi Fluorescence Spectrophotometer: F-7000). Electrochemical impedance spectroscopy (EIS) studies were conducted over a 3-electrode system (Metroohm AutoLab MAC90675) consisting of Pt wire, an Ag/AgCl electrode, and a working electrode prepared using a drop-casting method with 0.1 M Na 2 SO 4 as an electrolyte. 2.4.2 Reaction Sample Analysis Shimadzu UV–Vis spectrophotometer (UV 1900) was employed for the quantitative determination of all the PQ samples. The Total Organic Carbon (TOC-L, Shimadzu) of the samples before and after treatment was also determined. Further, the intermediates formed during the degradation process were identified using LCMS (Waters Alliance 2795) equipped with an electron spray ionization source (ESI). The run time for the samples was 10 min with an injection volume of 2 microlitres and a flow rate of 0.3 ml/min. Analysis was carried out using a C18 column with mobile phase as 0.1% formic acid in water and 0.1% formic acid in acetonitrile in the ratio of 20:80. 3. Results and Discussion 3.1 Characterization 3.1.1 Structural and Morphological Analysis 3.1.1.1 XRD The structural evolution of pristine and doped TiO 2 was determined with the XRD patterns depicted in Fig. 1 . The diffraction peaks present in the spectrum of PT are majorly indexed for anatase phase of TiO 2 with some rutile phases (00-021-1272) without any extra peak indicating the purity of the sample (El Mragui et al., 2021 ; Garg et al., 2022 , Pandey et al., 2023 ). It is also observed that with the introduction of guest species in the form of Fe (Fe-PT), Ni (Ni-PT), S (S-PT), C (C-PT), or Fe,S (Fe-S-PT) into the pores of PT, a substantial decrease in the intensity of anatase peaks took place marking the structural transformations in the anatase phase of TiO 2 . However, no extra peak corresponding to any metal/non-metal was detected which presumably happened because either all the guest ions were well incorporated into the crystal lattice or were well dispersed on the surface of PT (El Mragui et al., 2021 ). Another reason behind this observation could be the minimal amount of impurity added into crystal lattice of PT since peak is usually not encountered with dopant concentration lower than 5% (Kundu et al., 2014 ). Further, crystallite size (D) and interplanar distance (d), of all the nanocomposites were ascertained (Shaban et al., 2019 ) and are given in Table 1 . Table 1 Structural parameters of nanocomposites Sample 2θ d (Å) D (nm) PT 25.2442 3.52509 25.22 C-PT 25.3739 3.50734 23.18 Ni-PT 25.3072 3.51465 20.84 Fe-PT 24.9890 3.50104 14.84 S-PT 25.4204 3.56060 11.81 Fe-S-PT 25.3477 3.51091 11.12 3.1.1.2 FTIR To substantiate the presence of multiple functional groups, FTIR was performed in the range of 4000 − 500 cm − 1 . As outlined in Fig. 2 , broadband in the region of 3200–3600 cm − 1 attained for all composites recognized the presence of OH group attributing to its strong stretching vibration while sharp peak at 1600–1700 cm − 1 corresponds to bending vibration of O-H. Further, peaks in the rage of 500–800 cm − 1 arouse due to TiO 2 marking the attendance of Ti-O or Ti-O-Ti band (Wongcharoen & Panomsuwan, 2018 ; Zahedi et al., 2015 ). Moreover, no extra peak corresponding to guest species was observed providing another proof after XRD of proper incorporation of precursor ions into PT. 3.1.1.3 FESEM-EDX, Mapping and TEM Morphologies of synthesized heterostructures were evaluated using FESEM. Figure 3 (i-v) display the micrographs for pristine as well as modified nanostructures from which it can be seen that fine thread-like clusters were demonstrated by PT and Fe-PT also had thread-like structures delineating moss growth undersea. However, in case of S-PT, Ni-PT, and C-PT highly agglomerated spherical particles were observed. Thus, in order to collect a better insight into their structure, TEM of S-PT, Ni-PT, and C-PT were performed. As illustrated in Fig. 3 (vii-ix), Ni-PT and C-PT also depicted small thread-like arrangement and formed an assembly over PT (Kumar et al., 2018 ) while clear, large nanorod formation was visible for S-PT. Further, insight 3 (vi) showcase the successful deposition of Fe onto S-PT showcasing embedding of Fe onto nanorod linkages of S-PT. EDX (x-xv) establishes the purity of each nanocomposite as no extra peak apart from Ti, O, and respective precursor ion was observed in each case (Garg et al., 2022 ). Table 2 discusses the atomic% of constituents in each catalyst. After quantitative determination using EDX, qualitative determination of atomic composition for each nanomaterial at the surface level was evaluated using elemental mapping illustrated in Fig. S1 (a-e). Table 2 Elemental Analysis of Synthesised Nanomaterials a: EDX; b: XPS Sample Atomic % Actual % Ti a Ti b O a O b Precursor Ion a Precursor Ion b PT 31.38 31.47 68.62 68.53 - - - C-PT 30.63 31.80 68 66.75 1.37 1.45 1.5 Ni-PT 29.41 30.88 68.46 66.95 2.13 2.17 2.0 Fe-PT 31.70 30.27 66.63 68.34 1.67 1.39 1.5 S-PT 31.29 30.89 67.18 67.66 1.53 1.45 1.5 Fe-S-PT 32.28 30.36 64.68 66.84 1.60/1.44 1.41/1.39 1.5/1.5 3.1.1.4 Brunauer Emmett Teller (BET) Analysis Surface area has a key role towards activity of any catalyst as higher surface area is indicative of greater possibility of efficient degradation (Keerthana et al., 2022 ). Thus, to gain a detailed understanding of pore structure and surface area of nanocomposites, N 2 adsorption-desorption isotherm was performed. As featured in Fig. 4 , samples depicted Type IV adsorption along with H1 hysteresis corresponding to cylindrical-like pores demonstrating mesoporous nature of the material (ALOthman, 2012 ; Dong et al., 2011 ; Kaur et al., 2021 ). The surface area of synthesized PT came out to be much higher than those reported in literature for PQ degradation (Kanchanatip et al., 2011 ; Lenzi et al., 2021 ; Marien et al., 2017 ; Suwannaruang et al., 2018 ). Also, doped composites depicted higher surface area than PT since the addition of metal/nonmetal enhances surface roughness (Keerthana et al., 2022 ). Further, Barret-Joyner-Halenda (BJH) approach was adopted to determine the pore size and pore volume as summarised in Table 3 . Table 3 Textural and Optical properties of Nanocomposites Sample Surface Area (m 2 /g) Pore Size (nm) Pore Volume (cc/g) Band Gap Energy (eV) PT 112.231 9.31 0.596 3.24 C-PT 115.845 10.23 0.602 2.956 Ni-PT 121.067 10.62 0.620 2.876 Fe-PT 201.953 13.26 0.986 2.838 S-PT 246.234 14.59 1.146 2.608 Fe-S-PT 295.361 16.28 1.362 2.431 3.1.1.4 Identification of Surface Elemental Composition and Chemical States The elemental composition and chemical state were inspected using XPS technique which also provided the confirmation of doping as apart from Ti and O respective doped elements appeared in the XPS spectrum of the specific samples. Survey spectrum and deconvoluted spectra of all the doped catalysts are represented in Fig. 5 . In case of Ti, two peaks at 458.8eV and 464.6 eV were observed which correspond to Ti2p 3/2 and Ti2p 1/2 respectively (Tseng et al., 2009 ; Xiao et al., 2008 ). These peaks indicate the presence of Ti 4+ with no signal attributing to Ti 3+ confirming that Ti is absolutely in the Ti 4+ state (Kruanetr & Wanchanthuek, 2018 ). The core level of O1s was centred at 529.9eV, 530.4 eV, and 531.6 eV comprising of Ti-O-Ti, O-Ti, and O-H bonds respectively (Dong et al., 2011 ; Li et al., 2021 ; Tseng et al., 2009 ). In case of C-PT, survey spectrum contained sharp peaks of C(1s), Ti (2p), and O (1s) while deconvoluted C1s depicted three peaks. The peak at binding energy of 282.8 eV attributes to O-Ti-C in the literature while peaks at 284.3 eV and 288.6 eV are assigned to C-C and C-O respectively (Dong et al., 2011 ; Garg et al., 2022 ; Kang et al., 2008 ). Formation of O-Ti-C bond reveals the substitution of lattice O of TiO 2 by C atoms confirming the doping of C into TiO 2 (Dong et al., 2011 ). Ni-PT depicted peaks at 855.3 eV and 873.6 eV attributed to Ni2p 1/2 and Ni2p 3/2 respectively which divulge the presence of Ni 2+ immobilized into TiO 2 (Liu et al., 2015 ; Shaban et al., 2019 ). For S-PT, deconvoluted S2p gave characteristic peaks of S2p 3/2 and S2p 1/2 at 168.6eV and 169.9 eV respectively which are indicative of S 6+ and S 4+ ions (Li et al., 2021 ). These S 4+ ions could easily substitute the Ti 4+ ions of TiO 2 thus, incorporating S in TiO 2 lattice (Ni et al., 2016 ). Same is also justified by the XPS of S-PT showing distinctive peaks of S (2p), Ti (2p), and O (1s) providing suitable evidence of S doping into TiO 2 . The successful embedding of Fe into TiO 2 for Fe-PT is evident from XPS spectrum depicting the presence of Fe (2p), Ti (2p), and O (1s). Moreover, two broad peaks were present at 712 eV and 724 eV due to splitting of Fe2p core levels into Fe2p 3/2 and Fe2p 1/2 respectively. As per literature, these binding energies correspond to Fe 3+ species and thus suggest the doping of Fe in Fe 3+ state with no signal observed for Fe 2+ (Kruanetr et al., 2018; Kumar et al., 2018 ). Further, for Fe-S-PT; spectrum depicted the presence of Fe(2p), S (2p), Ti (2p), and O (1s) with Fe in Fe 3+ form and S as S 4+ ions. The atomic composition obtained for each catalyst is depicted in Table 2 and is found to be in good accordance with the composition acquired from EDX. 3.1.2 Optical Properties 3.1.2.1 UV-DRS Impact of doping on optical properties of nanomaterials was investigated using UV-DRS since optical activity is found to influence the photoactivity (Keerthana et al., 2022 ). The absorption response for all the materials was evaluated and is portrayed in Fig. 6 from which it could be stated that in comparison to PT, addition of impurity resulted in a shift in absorbance for all the doped catalysts to a higher wavelength in visible region. Additionally, the band gap energies of all the catalysts were deduced using tauc plot as delineated in Fig. 7 . (αhν) 2 vs energy curve was extrapolated to determine the band gap energy (E g ) for all the catalysts and a significant decrease in E g of PT with the introduction of foreign species could be seen which in turn justifies the proper dispersion of metal/non-metal impurities into PT (Garg et al., 2022 ; Nakhate et al., 2010 ). The band gap values are listed in Table 3 where the Eg of PT was reduced from 3.24 eV up to 2.431 eV in case of Fe-S-PT. This reduction in band gap with doping facilitates the utilization of synthesized nanomaterials under sunlight. 3.1.2.2 Photoluminescence (PL) Spectra Separation between the charge carriers and their recombination rate for all the fabricated materials was examined using PL analysis. As illustrated in Fig. 8 , a strong peak around 320 nm can be observed for all the materials which arise due to the recombination process of conduction band-valence band charge carriers however, a significant decline in peak intensities with the introduction of foreign species into TiO 2 is visible from the spectrum with the peak almost evanescing for Fe-S-PT (Dong et al., 2011 ). PL is a surface phenomenon that is indicative of recombination rate where high peak intensity corresponds to high recombination rate and thus providing a shorter life span to the generated electron-hole pair (Keerthana et al., 2022 ; Zangeneh et al., 2018 ). Significant reduction in the peaks with doping suggests that mixing of foreign species into TiO 2 can suppress the recombination of charge carriers and thus augment the separation between the carriers where Fe-S-PT with an almost flat peak delineate the most effective charge transfer to the target. 3.1.3 Photoelectrochemical Performance EIS analysis was performed to evaluate the photoelectrochemical performance of the synthesized nanomaterials by comprehending their charge transfer activity. The radius of the arc depicts the charge transfer capability where small the radius corresponds to lower transfer resistance of electrons at the surface resulting in a higher transfer of charge (Angela et al., 2021 ; Wang et al., 2022 ). It can be seen from Fig. 9 that with doping the arc radius showed a significant dwindle with minimum radius observed for Fe-S-PT. This denotes that Fe and S act as electron and hole acceptors respectively which aid in promoting the separation of electro-hole pairs thus providing an effective pathway to charge transfer (Li (a) et al., 2021). The obtained results are following the observation made in the PL study. 3.2 Photocatalytic Assessment 3.2.1 Preliminary Level Analysis Prior to the investigation of ability of synthesized materials to act as a photocatalyst, preliminary studies evaluating adsorption and photolytic behaviour in the presence and absence of UV light using PT as the catalyst was performed. All the experiments were carried out for 180 mins using 25 ppm PQ at natural pH of 6.3 under varied conditions unless stated otherwise. As validated from Fig. S2, both adsorption and photolysis resulted in minimal removal of 10% and 13% respectively. Moreover, the results revealed that with the introduction of UV light along with the catalyst, a sharp increase in the degradation percentage was achieved which however, decreased from 75–66% with sunlight. This observation can be associated with the high band gap energy of TiO 2 , making it active only under UV irradiation (Zangeneh et al., 2018 ). Thus, to attain maximum PQ degradation at minimal cost, modification of PT was carried out to make it solar active and various process parameters were optimized. 3.2.2. Role of doping and dopant concentrations Doping of TiO 2 with metal and/or nonmetal creates intra band gap levels which facilitate the reduction of band gap energy allowing the catalyst to perform under sunlight. Thus, PT was incorporated with Fe, Ni (metals), S, and C (nonmetals) and their effect on removal of PQ was evaluated under sunlight by varying the dopant concertation from 1.00 wt% to 2.50% with catalyst loading of 1 g/L. The change in degradation as a function of dopant concertation for each catalyst is depicted in Fig. 10 from which it can be ascertained that optimum values for Fe-PT, S-PT, and C-PT were 1.50 wt% while for Ni-PT 2.00 wt% depicted maximum efficiency. For each catalyst, PQ removal was found to increase with the increase in the dopant concentration up to a certain value due to the successful doping resulting in a reduced band gap however, this increase was then followed by a decrement. The reduction could be acknowledged by the reduction of the active surface sites on the catalyst (Varma et al., 2020 ). Moreover, amongst all the photocatalysts, 1.5% S-PT lead to maximum PQ removal. This observation is fully supported by the various characterizations performed as it has the lowest band gap energy along with a high surface area and small crystallite size. Further, in comparison to other photocatalysts, S-PT had lower electron-hole recombination as confirmed by the PL spectra. From the above analysis Fe came out as the optimum metal dopant while S was the optimum nonmetal dopant thus, further studies were performed for process optimization of 1.5% Fe-PT and 1.5% S-PT. 3.2.3. Role of varying catalyst loading Since the aim of the work is to develop an economically viable process of water treatment, the catalyst loading was optimized to achieve maximum possible degradation with the minimum usage of the catalyst. Assessments were done with catalyst loading ranging from 1.0 g/L to 2.0 g/L with the trends displayed in Fig. 11 . The PQ removal tendency increased till catalyst loading of 1.5 g/L and later declined which could be due to the turbidity enhancement of the solution hindering the light penetration into the solution. Also, high catalyst dosage could become the source of catalyst agglomeration leading to light scattering (Sraw et al., 2020 ). The results depict 87% PQ degradation with 1.5% Fe-PT and 93% PQ removal by 1.5% S-PT. 3.2.4. Effect of initial solution pH In order to get a deeper insight into the behaviour of the pollutant and photocatalyst, the effect of pH on degradation rate was evaluated. The pH was varied from acidic to a neutral range of 3–7 for both the catalysts using acetate buffer or buffer capsules while keeping all other conditions at optimum. The obtained trends are given in Fig. 12 where natural PQ pH of 6.3 was achieved as the optimum pH. The rate of pollutant removal from water strongly depends upon the pHzpc of the catalyst, pKa of the pollutant, and the interaction between the catalyst surface and the pollutant (Pourzad et al., 2020 ). For a solution having a pH lower than pKa, the cationic form of pollutant dominates. Similarly, in the case of catalyst; pH greater than pHzpc results in a negatively charged surface of the catalyst and vice-versa (M’Bra et al., 2019 ). For the given system, pKa of PQ is around 9 resulting in cationic form as dominant while pHzpc of both Fe-PT and S-PT is lower than 6.3 providing a negatively charged catalyst surface (Birben et al., 2016 ; M’Bra et al., 2019 ; Moein et al., 2020 ). This justifies pH 6.3 as the optimum pH since at this pH phenomenon of attraction between catalyst and pollutant surface occurs and several other studies have reported pH in the range of 5.9–6.5 as optimum (Pourzad et al., 2020 ). Variation in rate of PQ degradation with change in calcination temperature is discussed in supplementary file section 1 S with Fig. S3. 3.2.5 Activity of Metal-Nonmetal codoped TiO 2 Once both Fe-PT (metal doped) and S-PT (nonmetal doped) proved their individual efficacy as a solar active photocatalyst towards PQ degradation, Fe-S-PT-a codoped catalyst-was synthesized having nanorod like structure with large surface area and minimum recombination rate (as inferred from various analytical processes) and its photocatalytic behaviour was elucidated by keeping all other conditions at optimum as evaluated earlier i.e., 1.5% Fe doped into 1.5% S-PT, 1.5 g/L catalyst loading, pH 6.3 and calcination temperature 450ºC. One can observe from Fig. 13 that a significant enhancement of 10% in the rate of PQ degradation occurred from 87% with Fe-PT to 97% Fe-S-PT along with 30 mins of reduction in time which are attributed to the lowest electron-hole recombination rate of Fe-S-PT in contrast to Fe-PT or S-PT since lower recombination corresponds to a longer life span of charged species responsible for OH˙ generation which eventually carriers out the degradation process. 3.2.6 Evaluation of In-Situ Hybrid Process As discussed above in section 3.2.5 , co-doping of Fe and S into TiO 2 led to a significant increase in PQ degradation however, the process required a long period of around 3h which hampers its real-time application. For a process to be feasible at industrial scale, it must be cheap as well as less time-consuming. The implication of sunlight as the source of energy makes the process cheap however, efforts must be made toward reduction of process time. Henceforth, a hybrid process involving photocatalysis and photo-Fenton simultaneously was performed using Fe-S-PT where TiO 2 acts as the base for photocatalysis while Fe facilitates the photo-Fenton process in the presence of H 2 O 2 . The reaction was carried out under sunlight with 1.5 g/L of Fe-S-PT at pH 6.3 and H 2 O 2 500 uL/L and a sharp 47% decrement in the time required for PQ removal was encountered as given by Fig. 14 where instead of 150 mins, 80 mins were sufficient enough to degrade PQ. This observation is associated with the dual process taking place where Fe 3+ acts as the sink for the electrons generated at the conduction band of TiO 2 thus, preventing the electron-hole recombination and also generating OH˙ resulting in higher radical formation in comparison to the single photocatalysis process as explained below (Talwar et al., 2019 ). TiO 2 + hν → h + + e − (1) e − + O 2 + H 2 O → H 2 O + OH˙ (2) Fe 3+ + e- + H 2 O → Fe 2+ + H + + OH˙ (3) From the above analysis, it can be summarised that the hybrid process of photocatalysis and photo-Fenton provides a practically feasible real-life solution to the havoc of water pollution. 3.3 Kinetic Study and Synergistic Effect To carry out the kinetic study of Fe-S-PT as a photocatalyst as well as a dual catalyst; at first, the effect of initial PQ concentration on degradation was determined by varying the concentration from 5 ppm to 45 ppm since as per the Langmuir Hinshelwood Hougen Watson model (LHHW), the initial rate of degradation is a function of initial concentration (Sraw et al., 2018 ). As inferred from Fig. S4, initial concentration and degradation depicted an inverse relationship which was expected. Once the effect of initial concentration over degradation was determined, the kinetics was evaluated by plotting 1/r˳ vs 1/C˳. The obtained trend for both photocatalysis and dual process depicts a straight line as given in Fig. 15 which confirms the application of the LHHW model. The value of the rate constant (kr) for both processes was calculated as K photocatalysis = 0.93 mg/Lmin and K hybrid = 2.24 mg/Lmin. As expected, the rate constant for the dual process came out to be greater than the individual photocatalysis process. Further, the synergy of dual process over the discrete photocatalytic process was quantified as per the given equation (Talwar et al., 2019 )- % Synergy = {(K hybrid - K photocatalysis ) / K hybrid } * 100 (4) From the above equation, an increase of 58% in the reaction rate with the dual process marks the feasibility of this process and is due to a twofold reason i.e., the formation of hydroxyl radical is taking place not just by one process but due to multiple processes resulting in their production in abundance and further the utilization of electrons in the dual process makes the recombination infrequent. 3.4 Probable Mechanism The trapping experiments performed are discussed using Fig S5. Based on trapping studies one can state the degradation mechanism for the catalyst will mainly be governed by the OH˙ and e − . Prior to designing of mechanism, the potential values of conduction and valence bands were calculated using the relation (Kumar et al., 2018 )- E VB = X – E e + 0.5E g E CB = E VB - E g where; E VB : Potential of the valence band E CB : Potential of the conduction band X: Electronegativity of TiO 2 (~ 5.8 eV) E e : Energy of electrons (~ 4.5 eV) E g : Band gap energy Thus, for PT E VB = 2.92 eV and E CB = -0.32 eV. Further, on doping of Fe (metal) into PT fermi levels of CB would shift towards a positive value while the energy of VB will remain unchanged giving E VB = 2.92 eV and E CB = 0.082 eV. Similarly, on adding S (nonmetal) to PT VB will shift to higher energy while the energy for CB will remain unchanged giving E VB = 2.288 eV and E CB = -0.32 eV (Kang et al., 2008 ). Henceforth; on co-doping of Fe and S, both CB and VB will shift with Fe (doped as Fe 3+ ) acting as electron acceptor for generation of Fe 2+ and thus leading to the photo-Fenton process while at VB holes combine with water to generate OH˙ performing photocatalysis. This dual process of photocatalysis and photo-Fenton is outlined below by Scheme 1 . 3.5 Mineralization Study The purpose of the study is not just the removal of PQ from water but also to break down this complex structure into a simpler, nontoxic product. This was ensured by the determination of C content reduced with time using TOC analysis. Figure 16 illustrates the extent of mineralization undergone by PQ during degradation via a hybrid process of 25 ppm solution at pH 6.3 and 1.5 g/L of Fe-S-PT and was calculated to be 87% in 80 mins only. Against this 87% TOC removal, literature has reported 27.45% TOC elimination of 10 ppm PQ via photocatalysis under UV illumination (M’Bra et al., 2019 ) and 50% for 150 ppm solution after 300 mins of UV irradiation (Moctezuma et al., 2006 ). A detailed comparison of the present work with the literature is provided in Table 4 below. Table 4 Comparative Study for Degradation of PQ Catalyst Process Energy Source pH Time (mins) % TOC % Degradation Reference 1%Fe-1%Ti/SiO 2 Photocatalysis Sunlight 7 60 - 67 (Kruanetr & Wanchanthuek, 2018 ) N-TiO 2 Photocatalysis Visible 5.5 120 - 61.72 (Suwannaruang et al., 2018 ) BCBF CBF Photocatalysis Sunlight 7.2 120 - 84.5 52.1 (Kumar et al., 2018 ) Ce-TNTs Photocatalysis UV - 240 51.1 80.8 (Eleburuike et al., 2016 ) Fe 2+ /H 2 O 2 Fenton Dark 3 240 40 100 (Santos et al., 2011 ) TiO 2 Photocatalysis UV 10 90 37.5 66.3 (Phuinthiang & Kajitvichyanukul, 2019 ) Fe 2+ /H 2 O 2 Photo-Fenton UV - 60 64.6 - (Trovó et al., 2013 ) Fe-S-PT Hybrid Sunlight 6.3 80 87 97 This Study 3.6 Intermediates Formed Apart from mineralization studies, breaking down of PQ into simpler compounds via hyrid process was further justified by performing the LCMS of the solution at various time intervals and the obtained peaks are given in Fig S6. The major characteristics peak for untreated PQ were observed at m/z 144 (4%), 171 (100%), 185 (80%) and 186 (50%) where m/z = 186 corresponds to cationic paraquat without chloride ions while demthylation from cationic paraquat results into the ion fragment of m/z = 171 (Florêncio et al., 2004 ; Marien et al., 2019 ). Moreover, the fragmentation of m/z = 186 gives m/z = 185 monocation fragment which on loss of -CH 3 CN yields m/z = 144 (Evans et al., 2001 ; Florêncio et al., 2004 ). After performing hyrid process for 30 mins, multiple peaks indicative of PQ breakdown was observed at m/z = 216 (2%), 201 (7%), 172 (10%), 170 (3%), and 158 (10%) apart from prior obtained peaks at 171 (100%), 185 (29%) and 186 (8%) (Evans et al., 2001 ; Florêncio et al., 2004 ; Marien et al., 2019 ). Further, after 55 mins almost all of the above obtained peaks disappeared with only m/z = 94 (15%), 158 (8%), 185 (5%) and 216 (27%) remaining. Formation and removal of major peaks confirms these species to be intermediates during the process. Furthermore, disappearance of the peaks associated with PQ (m/z = 144, 171, 186) or decline in their peak intensity (m/z = 185) marks the removal of PQ from the solution while increase in the intensity for m/z = 216 shows the formation of new product i.e. dipyridone which is less toxic than PQ (Cartaxo et al., 2015 ). Finally at the end of the process, m/z = 94 (8%) and 216 (16%) were only present depicting degradation of complex PQ into simpler and less toxic species which are better for the environment. The probable degradation pathway of PQ is depicted in scheme 2 . 4. Conclusion In this study, PT along with metal and nonmetal modified TiO 2 was synthesized using hydrothermal treatment and employed for degradation of PQ under UV and sunlight. Investigation of their optical and morphological properties indicated that with the introduction of metal or nonmetal in TiO 2 lattice enhancement in its properties occurred with S-PT depicting lowest and gap energy, high surface area and growth of nanorods. Moreover, this 1.5%S-PT performed as an excellent photocatalyst resulting in 93% PQ removal followed by 1.5%Fe-PT degrading 87% PQ. However, with aim of reducing reaction time and attaining a higher degradation rate, Fe-S-PT codoped catalyst was prepared and a dual process of simultaneous photocatalysis and photo-Fenton was carried out. A sharp decrement of 47% in the process time was attained with this hybrid process along with synergy of 71%. The trapping experiments declared OH˙ and e − as the active species based on which the degradation mechanism was designed. Mineralization of 87% in 80 mins indicated the conversion of complex PQ into simpler and non-toxic forms which was further proved by the LCMS investigating various intermediates formed. The present study overall has the economical real-time application of degrading PQ within 80 mins utilizing freely available sunlight at the benign pH of 6.3. Declarations Acknowledgments Yamini Pandey would like to thank Jawaharlal Nehru Memorial Fund, New Delhi for providing scholarship to carry out research work. All the authors also acknowledge TEQIP-III (Dr. SSB UICET, Panjab University, Chandigarh) for giving financial assistance during this work. We also recognize Central Instrumentation Facility (CIL) and SAIF, Panjab University for performing various characterization and analytical analyses. Authors Contributions Yamini Pandey: Data curation, Formal analysis, Investigation, Writing – original draft, preparation. Aarsee Dhindsa: Reviewing. Anoop Verma: Supervision, Methodology, Reviewing. Amrit Pal Toor: Visualization, Conceptualization, Supervision, Validation. Competing Interests All authors hereby declare that they do not have any competing financial or personal interests. Data and Code Availability Not applicable Supplementary Information Supplementary data file attached separately. Ethical Approval This is inapplicable Consent to Participate This is inapplicable Consent to Publish The manuscript may be published by the journal with the approval of all authors. Funding This research receives no external funding. Availability of data and materials All the necessary data has been provided in the manuscript; any additional data required may be provided on demand. References ALOthman, Z. A. (2012). A review: fundamental aspects of silicate mesoporous materials. Materials, 5(12), 2874-2902. Angela, S., Lunardi, V. B., Kusuma, K., Soetaredjo, F. E., Putro, J. N., Santoso, S. P., ... & Ismadji, S. (2021). 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Schemes Schemes 1 and 2 are available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files SupplSpringer.docx scheme1.png Scheme 1: Probable Degradation Mechanism of PQ using Fe-S-PT scheme2.png Scheme 2: Probable Pathway followed by PQ for Degradation using Hybrid Process Cite Share Download PDF Status: Posted Version 1 posted 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. 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TiO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/f696bea8366060af612057b7.png"},{"id":50540379,"identity":"52513862-7996-42a6-b7b7-eff128be6400","added_by":"auto","created_at":"2024-02-02 06:41:57","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":136217,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eFTIR spectra of synthesized nanocomposites\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/a77c1a91035b4c5e50fe3c81.png"},{"id":50539717,"identity":"6936f602-cf16-40f0-9293-e30ef04e2ef5","added_by":"auto","created_at":"2024-02-02 06:25:57","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":816181,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(i-vi) FESEM micrographs, (vii-ix) TEM images, (x-xv) EDX spectra\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/bed5d4c2fbae5b00b0497df6.png"},{"id":50539714,"identity":"e8d05b0b-dc86-4de7-ab9f-52db0d5561e6","added_by":"auto","created_at":"2024-02-02 06:25:57","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":101067,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eN\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e Physisorption Isotherm\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/217a01616106bad9aa00b9f7.png"},{"id":50539502,"identity":"f9ff7d0b-be12-4164-bd91-9fc38a5001d6","added_by":"auto","created_at":"2024-02-02 06:17:57","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":300259,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eXPS Spectrum of doped TiO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/e369f978cbf06149d6b90e6f.png"},{"id":50539723,"identity":"39fd4a2f-8e08-4a32-a198-24d8dc02ebd9","added_by":"auto","created_at":"2024-02-02 06:25:57","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":75756,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAbsorption Spectra of Synthesised Catalysts\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/fc869ca5f7a5e7d67ec42adf.png"},{"id":50540033,"identity":"dad962ae-57f9-4217-a6ad-ddb914029dab","added_by":"auto","created_at":"2024-02-02 06:33:57","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":98168,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTauc’s Plot of Synthesised Catalysts\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/612549af41fc4bdb8fb0b16f.png"},{"id":50539503,"identity":"94640d8f-7404-43d8-876c-933f0801bfe9","added_by":"auto","created_at":"2024-02-02 06:17:57","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":74318,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePL Spectra of Fabricated Photocatalysts\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/6951d3dcbc9d5551d2c85e3d.png"},{"id":50539716,"identity":"1c49dfe8-f874-4357-8dd6-44660fcf51b8","added_by":"auto","created_at":"2024-02-02 06:25:57","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":88720,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eNyquist Plot for EIS of pristine and doped TiO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/c2eb9745d3fe5117edd16518.png"},{"id":50540037,"identity":"24cd442c-dd51-4448-8229-fdc4b047af88","added_by":"auto","created_at":"2024-02-02 06:33:57","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":35092,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eEffect of varying dopant concertation on PQ removal (Sunlight, PQ 25 ppm, pH 6.3, Catalyst Loading 1g/L, Time 180 mins)\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/995a8f43f10cfab4e505c138.png"},{"id":50539507,"identity":"f549f8f6-bcbe-486c-833b-67b1300891ce","added_by":"auto","created_at":"2024-02-02 06:17:57","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":23646,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eChange in rate of PQ degradation with varying catalyst loading (Sunlight, PQ 25 ppm, pH 6.3, Time 180 mins)\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"11.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/6428ce87cc89bcd0369e6569.png"},{"id":50540378,"identity":"77468d26-3868-4841-9be8-c60a05390d31","added_by":"auto","created_at":"2024-02-02 06:41:57","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":23950,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eChange in PQ degradation with change in pH (Sunlight, PQ 25 ppm, pH 6.3, Catalyst Loading 1.5g/L, Time 180 mins)\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"12.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/d0d3e599efd669d970c37d16.png"},{"id":50539512,"identity":"687b4fec-cb0d-4bf8-bc67-ac20ba6c7060","added_by":"auto","created_at":"2024-02-02 06:17:57","extension":"png","order_by":13,"title":"Figure 13","display":"","copyAsset":false,"role":"figure","size":30088,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eEnhancement in degradation rate of PQ with codoped TiO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e (Sunlight, PQ 25 ppm, pH 6.3, Catalyst Loading 1.5 g/L)\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"13.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/23e756e44f1da9f799d3b0c2.png"},{"id":50539510,"identity":"9f162586-f3bf-45e4-8dbe-193fe0e2edd1","added_by":"auto","created_at":"2024-02-02 06:17:57","extension":"png","order_by":14,"title":"Figure 14","display":"","copyAsset":false,"role":"figure","size":13426,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eEfficiency of Hybrid Process over Photocatalysis for degradation of PQ (Sunlight, PQ 25 ppm, pH 6.3, Fe-S-PT, Catalyst Loading 1.5 g/L)\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"14.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/82c4e1accd6b5cc9b6a774dc.png"},{"id":50540038,"identity":"eaecaca3-d1d7-42fb-913a-92498475ec0e","added_by":"auto","created_at":"2024-02-02 06:33:57","extension":"png","order_by":15,"title":"Figure 15","display":"","copyAsset":false,"role":"figure","size":13252,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eLHHW relation for PQ degradation using Photocatalysis and Hybrid Process\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"15.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/640f6c8307ad9ad182fd3897.png"},{"id":50539515,"identity":"4402a3b9-ad32-49b0-8197-ab51355abb7d","added_by":"auto","created_at":"2024-02-02 06:17:57","extension":"png","order_by":16,"title":"Figure 16","display":"","copyAsset":false,"role":"figure","size":18515,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eExtent of mineralization of PQ using Fe-S-PT\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"16.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/5b2178e2500fe32e225c42cf.png"},{"id":51268894,"identity":"fa8cc1f0-1e40-4697-914d-5952d8ec0f64","added_by":"auto","created_at":"2024-02-17 15:37:39","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2118832,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/0500f494-7ed5-42e0-8efe-1b87be2f5d16.pdf"},{"id":50540034,"identity":"4025b302-af66-44c6-8b21-63f4a04a4bb3","added_by":"auto","created_at":"2024-02-02 06:33:57","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1730673,"visible":true,"origin":"","legend":"","description":"","filename":"SupplSpringer.docx","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/8fff96238ff31c5eb2da2d07.docx"},{"id":50539497,"identity":"50140e06-108f-48c9-a6f0-e8d1acb8be77","added_by":"auto","created_at":"2024-02-02 06:17:57","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":67944,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1: Probable Degradation Mechanism of PQ using Fe-S-PT\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/0f177706bfc3ccad72991a3d.png"},{"id":50539722,"identity":"bc124af8-1df6-4ffb-aca3-9c9780e722d7","added_by":"auto","created_at":"2024-02-02 06:25:57","extension":"png","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":77529,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 2: Probable Pathway followed by PQ for Degradation using Hybrid Process\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"scheme2.png","url":"https://assets-eu.researchsquare.com/files/rs-3909915/v1/298d614a33a1471a6ed0c45c.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"Elucidating Synergistic Effect of In-Situ Hybrid Process Towards Paraquat Abatement","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eWith every passing day world is moving towards development however, this development comes at the cost of environment. Rapid growth of population along with urbanization and industrialization results in pollution ranging from air to water to soil with water pollution emerging as a major societal challenge accelerating at the same pace as that of industries and human society. Contamination of water bodies with chemicals is no longer a hidden truth with agricultural activities, pharmaceutical, cosmetics, tannery, and dyes being the major contributors (Marien et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). Amongst various effluents, pesticides/herbicides from agriculture practices act as the prominent contaminants. The property of these materials being toxic as well as non-biodegradable in nature makes the situation even worse.\u003c/p\u003e \u003cp\u003eParaquat (PQ) is one such extensively used herbicide leaving behind both health and environmental hazards. Its fast adsorption onto leaves, high solubility in water, recalcitrant nature along with resistance towards microbial degradation makes it a subject of concern (Florenci et al., 2004; Moctezuma et al., \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e1999\u003c/span\u003e). Therefore, it is required to carry out commercial management of pesticides keeping strict control over their application which in itself is a challenge as with the increase in population need for high-quality crops is increasing. So, the most promising alternative is to perform their degradation into simpler and non-toxic species which are safe for the environment.\u003c/p\u003e \u003cp\u003ePesticides can be degraded either by microbial action or by employing Advanced Oxidation Process (AOP). However, microbial action faces a major drawback i.e., it is a very slow process (Moctezuma et al., \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e1999\u003c/span\u003e) and pesticides like PQ are resistant to microbial degradation limiting their application towards depolluting wastewater. Contrary to this, AOP is a practical, powerful and impactful approach toward water remediation which is a sustainable cum greener technology (Kumar et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Photocatalysis is a widely explored AOP technique characterized with production of highly reactive OH˙ which is unselective in nature and performs degradation at room temperature (Bianco et al., 2005; Cantavenera et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2007\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eAmong variety of photocatalysts, TiO\u003csub\u003e2\u003c/sub\u003e is substantially explored owing to its characteristic features-low cost, high photosensitivity, non-toxic, and innocuous. However, single photocatalysis involving TiO\u003csub\u003e2\u003c/sub\u003e suffers major drawbacks-limited spectrum activation resulting in low quantum yield in visible region and rapid recombination of photocarriers, questioning its photocatalytic performance (Suwannaruang et al., \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). As a result, formation of heterojunction comes to rescue which enhances separation efficiency of photocarriers along with photo response of the catalyst allowing to harvest freely available sunlight making the process sustainable, greener, and economical (Swain \u0026amp; Basu, \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Variety of literature discusses the positive effect of doping TiO\u003csub\u003e2\u003c/sub\u003e with metal or nonmetal towards the inhibition of organic pollutants from water (Damacena et al., \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Dong et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; El Mragui et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Keerthana et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Kundu et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Nakhate et al., \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2010\u003c/span\u003e; Shaban et al., \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e2019\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eApart from photocatalysis, photo-Fenton is another type of AOP where Fe\u003csup\u003e2+\u003c/sup\u003e/Fe\u003csup\u003e3+\u003c/sup\u003e reacts with H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e under highly acidic pH conditions for generation of OH˙ (Phan et al., 2023). But; unfortunately, AOP at commercial scale is still in limbo due to stumbling blocks like costly dopant synthesis, difficulty in catalyst separation, long treatment time, iron sludge formation, high dosage of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, requirement of highly acidic conditions (Ncube et al., \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Talwar et al., \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Thakur \u0026amp; \u0026Ouml;rmeci, \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Hence, it is a challenge to replace traditional AOP with commercially viable and economical process.\u003c/p\u003e \u003cp\u003eIn the quest of monitoring PQ, emphasis has been on the role of pure or modified TiO\u003csub\u003e2\u003c/sub\u003e but majorly involves utilization of UV or visible light (Cantavenera et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Eleburuike et al., \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Flor\u0026ecirc;ncio et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2004\u003c/span\u003e; Suwannaruang et al., \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Few works also investigated Fenton/Photo-Fenton process towards PQ removal however two major challenges i.e., high acidic environment and high H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e dosage pertain (Oliveira et al., \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Santos et al., \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Trov\u0026oacute; et al., \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). Along with these drawbacks, another issue of high reaction time is consistent making the practical application of the process questionable (Cantavenera et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Eleburuike et al., \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Marien et al., \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Santos et al., \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). Moreover, research prominently lacks the knowledge of various active species responsible for PQ degradation which hinders getting exact knowledge of the mechanism followed by the catalysts.\u003c/p\u003e \u003cp\u003eConsidering all the above-discussed gaps, this study involves modification of electronic structure of TiO\u003csub\u003e2\u003c/sub\u003e intending to compare the effect of metal and non-metal incorporation towards PQ abatement under sunlight. Moreover, with primary focus on providing an industrially viable solution coping with all the drawbacks of the individual processes, an in-situ hybrid technique involving photocatalysis and photo-Fenton is carried out which to the best of our knowledge is first such study on PQ. Further investigations involve the study of structural and optical properties of samples along with mechanistic properties for determination of major active species. The extent of mineralization and kinetics of the model pollutant have also been discussed giving a clear insight into the mechanism followed for PQ removal along with various intermediates formed throughout the process.\u003c/p\u003e"},{"header":"2. Experimental Procedure","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Materials\u003c/h2\u003e \u003cp\u003ePQ (98% pure) was acquired from Sigma Aldrich. Glacial acetic acid and sodium acetate used for making buffers was supplied by CDH. TiO\u003csub\u003e2\u003c/sub\u003e was purchased from Evonik India and 30% (v/v) H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e from CDH. NaOH pellets, nickel nitrate heptahydrate, thiourea, graphite, and ferrous nitrate nona hydrate were supplied by Loba Chemie. Scavenger studies were performed using isopropyl alcohol (IPA) and sodium chloride acquired from CDH, silver nitrate supplied by Sigma Aldrich, and 1,4-p-benzoquinone (p-BQ) from TCI. Preparation for all solutions was done using distilled water.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Nanocomposite Synthesis\u003c/h2\u003e \u003cp\u003ePT and all other photocatalysts were synthesized hydrothermally with P25 TiO\u003csub\u003e2\u003c/sub\u003e as the precursor. PT synthesis involved dispersion of 2g P25 TiO\u003csub\u003e2\u003c/sub\u003e into 100 mL NaOH (10 M) followed by vigorous stirring and thus obtained homogenized solution was placed into a Teflon lined autoclave for hydrothermal treatment at 150˙C for 12 h. The precipitate was then cooled, filtered, and subjected to multiple washings with HCl (1M) and distilled water till neutral pH was attained. The obtained powder was then oven dried and calcined at 450˙C for 3 h.\u003c/p\u003e \u003cp\u003eSimilar procedure was followed for amalgamating Fe-PT, Ni-PT, S-PT, and C-PT by stirring the required amount of metal/nonmetal precursor and PT and then subjecting the mixture to hydrothermal treatment. The precursor for Fe, Ni, S, and C was ferrous nitrate nona hydrate, nickel nitrate heptahydrate, thiourea, and graphite powder respectively. Fe-S-PT synthesis involved the incorporation of Fe into the above prepared S-PT via hydrothermal process.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Protocol for Evaluating Degradation Activity\u003c/h2\u003e \u003cp\u003ePhotocatalytic experiments involving UV irradiation were carried out in a UV chamber having 8 blue-black UV (365 nm) tubes on top of the chamber and magnetic stirrer at the bottom over which a hemispherical slurry reactor was placed. For performing reactions under sunlight, similar setup was used without any chamber. Moreover, for hybrid process under sunlight; the same setup was provided with air spargers and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e was added prior to the reaction. After every fixed time interval sample was collected, filtered using 0.22 \u0026micro;m microfilters, and then analyzed using UV-Vis spectrophotometer.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Instrumentation and Analytical Determinations\u003c/h2\u003e \u003cdiv id=\"Sec7\" class=\"Section3\"\u003e \u003ch2\u003e2.4.1 Catalyst Characterization\u003c/h2\u003e \u003cp\u003eIn order to investigate the various phases of the synthesized photocatalysts, a powder X-ray Diffractometer (XRD) analyzer (Pan analytical X\u0026rsquo;Pert Pro diffractometer (D/max rA) at 45 kV and 40 mA with Cu (Kα\u0026thinsp;=\u0026thinsp;1.504060 Ǻ) in the range of 2θ\u0026thinsp;=\u0026thinsp;20\u0026deg;\u0026ndash;90\u0026deg; was used. The Fourier transform infrared (FT-IR) spectrum of all the materials was measured in the range of 4000\u0026thinsp;\u0026minus;\u0026thinsp;600 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e using Spectrum RX-I. To analyze the structural morphology as well as the chemical composition of the catalysts, a field emission scanning electron microscope (FE-SEM) (Zeiss EV050) equipped with energy dispersive X-ray (EDX) (Bruker AXS, QuanTax 20) was used. The surface composition of the materials was acquired with X-ray Photoelectron Spectroscopy (XPS) on Physical Electronics-PHI 5000 VersaProbe III-ESCA system. The BET analysis of the surface area, pore volume, and pore size were studied using Quantachrome Autosorb 1 analyzer.\u003c/p\u003e \u003cp\u003eThe optical properties were further studied using multiple analytical techniques. The band gap energy of all the photocatalysts was compared using UV-DRS (Shimadzu UV\u0026ndash;Vis spectrophotometer-UV 2400) with BaSO\u003csub\u003e4\u003c/sub\u003e as a reference. Further, the rate of electron-hole recombination was determined by photoluminescence (PL) spectra (Hitachi Fluorescence Spectrophotometer: F-7000).\u003c/p\u003e \u003cp\u003eElectrochemical impedance spectroscopy (EIS) studies were conducted over a 3-electrode system (Metroohm AutoLab MAC90675) consisting of Pt wire, an Ag/AgCl electrode, and a working electrode prepared using a drop-casting method with 0.1 M Na\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e as an electrolyte.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section3\"\u003e \u003ch2\u003e2.4.2 Reaction Sample Analysis\u003c/h2\u003e \u003cp\u003eShimadzu UV\u0026ndash;Vis spectrophotometer (UV 1900) was employed for the quantitative determination of all the PQ samples. The Total Organic Carbon (TOC-L, Shimadzu) of the samples before and after treatment was also determined. Further, the intermediates formed during the degradation process were identified using LCMS (Waters Alliance 2795) equipped with an electron spray ionization source (ESI). The run time for the samples was 10 min with an injection volume of 2 microlitres and a flow rate of 0.3 ml/min. Analysis was carried out using a C18 column with mobile phase as 0.1% formic acid in water and 0.1% formic acid in acetonitrile in the ratio of 20:80.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Characterization\u003c/h2\u003e \u003cdiv id=\"Sec11\" class=\"Section3\"\u003e \u003ch2\u003e3.1.1 Structural and Morphological Analysis\u003c/h2\u003e \u003cdiv id=\"Sec12\" class=\"Section4\"\u003e \u003ch2\u003e3.1.1.1 XRD\u003c/h2\u003e \u003cp\u003eThe structural evolution of pristine and doped TiO\u003csub\u003e2\u003c/sub\u003e was determined with the XRD patterns depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The diffraction peaks present in the spectrum of PT are majorly indexed for anatase phase of TiO\u003csub\u003e2\u003c/sub\u003e with some rutile phases (00-021-1272) without any extra peak indicating the purity of the sample (El Mragui et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Garg et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2022\u003c/span\u003e, Pandey et al., \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). It is also observed that with the introduction of guest species in the form of Fe (Fe-PT), Ni (Ni-PT), S (S-PT), C (C-PT), or Fe,S (Fe-S-PT) into the pores of PT, a substantial decrease in the intensity of anatase peaks took place marking the structural transformations in the anatase phase of TiO\u003csub\u003e2\u003c/sub\u003e. However, no extra peak corresponding to any metal/non-metal was detected which presumably happened because either all the guest ions were well incorporated into the crystal lattice or were well dispersed on the surface of PT (El Mragui et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Another reason behind this observation could be the minimal amount of impurity added into crystal lattice of PT since peak is usually not encountered with dopant concentration lower than 5% (Kundu et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2014\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFurther, crystallite size (D) and interplanar distance (d), of all the nanocomposites were ascertained (Shaban et al., \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e2019\u003c/span\u003e) and are given in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eStructural parameters of nanocomposites\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2θ\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003ed (\u0026Aring;)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eD (nm)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e25.2442\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3.52509\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e25.22\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e25.3739\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3.50734\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e23.18\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNi-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e25.3072\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3.51465\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e20.84\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e24.9890\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3.50104\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e14.84\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eS-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e25.4204\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3.56060\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e11.81\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe-S-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e25.3477\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3.51091\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e11.12\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section4\"\u003e \u003ch2\u003e3.1.1.2 FTIR\u003c/h2\u003e \u003cp\u003eTo substantiate the presence of multiple functional groups, FTIR was performed in the range of 4000\u0026thinsp;\u0026minus;\u0026thinsp;500 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. As outlined in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, broadband in the region of 3200\u0026ndash;3600 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e attained for all composites recognized the presence of OH group attributing to its strong stretching vibration while sharp peak at 1600\u0026ndash;1700 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponds to bending vibration of O-H. Further, peaks in the rage of 500\u0026ndash;800 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e arouse due to TiO\u003csub\u003e2\u003c/sub\u003e marking the attendance of Ti-O or Ti-O-Ti band (Wongcharoen \u0026amp; Panomsuwan, \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Zahedi et al., \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). Moreover, no extra peak corresponding to guest species was observed providing another proof after XRD of proper incorporation of precursor ions into PT.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section4\"\u003e \u003ch2\u003e3.1.1.3 FESEM-EDX, Mapping and TEM\u003c/h2\u003e \u003cp\u003eMorphologies of synthesized heterostructures were evaluated using FESEM. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (i-v) display the micrographs for pristine as well as modified nanostructures from which it can be seen that fine thread-like clusters were demonstrated by PT and Fe-PT also had thread-like structures delineating moss growth undersea. However, in case of S-PT, Ni-PT, and C-PT highly agglomerated spherical particles were observed. Thus, in order to collect a better insight into their structure, TEM of S-PT, Ni-PT, and C-PT were performed. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (vii-ix), Ni-PT and C-PT also depicted small thread-like arrangement and formed an assembly over PT (Kumar et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2018\u003c/span\u003e) while clear, large nanorod formation was visible for S-PT. Further, insight 3 (vi) showcase the successful deposition of Fe onto S-PT showcasing embedding of Fe onto nanorod linkages of S-PT.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eEDX (x-xv) establishes the purity of each nanocomposite as no extra peak apart from Ti, O, and respective precursor ion was observed in each case (Garg et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e discusses the atomic% of constituents in each catalyst. After quantitative determination using EDX, qualitative determination of atomic composition for each nanomaterial at the surface level was evaluated using elemental mapping illustrated in Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e (a-e).\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003e\u003cb\u003eElemental Analysis of Synthesised Nanomaterials\u003c/b\u003e a: EDX; b: XPS\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"8\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"6\" nameend=\"c7\" namest=\"c2\"\u003e \u003cp\u003eAtomic %\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eActual %\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTi\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eTi\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eO\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eO\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003ePrecursor Ion\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003ePrecursor Ion\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e31.38\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e31.47\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e68.62\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e68.53\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e30.63\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e31.80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e68\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e66.75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.37\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNi-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e29.41\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e30.88\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e68.46\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e66.95\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.17\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e2.0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e31.70\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e30.27\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e66.63\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e68.34\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.67\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.39\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eS-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e31.29\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e30.89\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e67.18\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e67.66\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.53\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe-S-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e32.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e30.36\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e64.68\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e66.84\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.60/1.44\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.41/1.39\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.5/1.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section4\"\u003e \u003ch2\u003e\u003cb\u003e3.1.1.4 Brunauer Emmett Teller (BET) Analysis\u003c/b\u003e\u003c/h2\u003e \u003cp\u003eSurface area has a key role towards activity of any catalyst as higher surface area is indicative of greater possibility of efficient degradation (Keerthana et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Thus, to gain a detailed understanding of pore structure and surface area of nanocomposites, N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption isotherm was performed. As featured in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e, samples depicted Type IV adsorption along with H1 hysteresis corresponding to cylindrical-like pores demonstrating mesoporous nature of the material (ALOthman, \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Dong et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Kaur et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). The surface area of synthesized PT came out to be much higher than those reported in literature for PQ degradation (Kanchanatip et al., \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Lenzi et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Marien et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Suwannaruang et al., \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Also, doped composites depicted higher surface area than PT since the addition of metal/nonmetal enhances surface roughness (Keerthana et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Further, Barret-Joyner-Halenda (BJH) approach was adopted to determine the pore size and pore volume as summarised in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eTextural and Optical properties of Nanocomposites\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSurface Area (m\u003csup\u003e2\u003c/sup\u003e/g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePore Size (nm)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePore Volume (cc/g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eBand Gap Energy (eV)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e112.231\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e9.31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.596\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e3.24\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e115.845\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e10.23\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.602\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.956\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNi-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e121.067\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e10.62\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.620\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.876\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e201.953\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e13.26\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.986\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.838\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eS-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e246.234\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e14.59\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.146\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.608\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe-S-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e295.361\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e16.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.362\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2.431\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section4\"\u003e \u003ch2\u003e3.1.1.4 Identification of Surface Elemental Composition and Chemical States\u003c/h2\u003e \u003cp\u003eThe elemental composition and chemical state were inspected using XPS technique which also provided the confirmation of doping as apart from Ti and O respective doped elements appeared in the XPS spectrum of the specific samples.\u003c/p\u003e \u003cp\u003eSurvey spectrum and deconvoluted spectra of all the doped catalysts are represented in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. In case of Ti, two peaks at 458.8eV and 464.6 eV were observed which correspond to Ti2p\u003csub\u003e3/2\u003c/sub\u003e and Ti2p\u003csub\u003e1/2\u003c/sub\u003e respectively (Tseng et al., \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Xiao et al., \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2008\u003c/span\u003e). These peaks indicate the presence of Ti\u003csup\u003e4+\u003c/sup\u003e with no signal attributing to Ti\u003csup\u003e3+\u003c/sup\u003e confirming that Ti is absolutely in the Ti\u003csup\u003e4+\u003c/sup\u003e state (Kruanetr \u0026amp; Wanchanthuek, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). The core level of O1s was centred at 529.9eV, 530.4 eV, and 531.6 eV comprising of Ti-O-Ti, O-Ti, and O-H bonds respectively (Dong et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Li et al., \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Tseng et al., \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e2009\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIn case of C-PT, survey spectrum contained sharp peaks of C(1s), Ti (2p), and O (1s) while deconvoluted C1s depicted three peaks. The peak at binding energy of 282.8 eV attributes to O-Ti-C in the literature while peaks at 284.3 eV and 288.6 eV are assigned to C-C and C-O respectively (Dong et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Garg et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Kang et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2008\u003c/span\u003e). Formation of O-Ti-C bond reveals the substitution of lattice O of TiO\u003csub\u003e2\u003c/sub\u003e by C atoms confirming the doping of C into TiO\u003csub\u003e2\u003c/sub\u003e (Dong et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). Ni-PT depicted peaks at 855.3 eV and 873.6 eV attributed to Ni2p\u003csub\u003e1/2\u003c/sub\u003e and Ni2p\u003csub\u003e3/2\u003c/sub\u003e respectively which divulge the presence of Ni\u003csup\u003e2+\u003c/sup\u003e immobilized into TiO\u003csub\u003e2\u003c/sub\u003e (Liu et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2015\u003c/span\u003e; Shaban et al., \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e2019\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eFor S-PT, deconvoluted S2p gave characteristic peaks of S2p\u003csub\u003e3/2\u003c/sub\u003e and S2p\u003csub\u003e1/2\u003c/sub\u003e at 168.6eV and 169.9 eV respectively which are indicative of S\u003csup\u003e6+\u003c/sup\u003e and S\u003csup\u003e4+\u003c/sup\u003e ions (Li et al., \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). These S\u003csup\u003e4+\u003c/sup\u003e ions could easily substitute the Ti\u003csup\u003e4+\u003c/sup\u003e ions of TiO\u003csub\u003e2\u003c/sub\u003e thus, incorporating S in TiO\u003csub\u003e2\u003c/sub\u003e lattice (Ni et al., \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). Same is also justified by the XPS of S-PT showing distinctive peaks of S (2p), Ti (2p), and O (1s) providing suitable evidence of S doping into TiO\u003csub\u003e2\u003c/sub\u003e. The successful embedding of Fe into TiO\u003csub\u003e2\u003c/sub\u003e for Fe-PT is evident from XPS spectrum depicting the presence of Fe (2p), Ti (2p), and O (1s). Moreover, two broad peaks were present at 712 eV and 724 eV due to splitting of Fe2p core levels into Fe2p\u003csub\u003e3/2\u003c/sub\u003e and Fe2p\u003csub\u003e1/2\u003c/sub\u003e respectively. As per literature, these binding energies correspond to Fe\u003csup\u003e3+\u003c/sup\u003e species and thus suggest the doping of Fe in Fe\u003csup\u003e3+\u003c/sup\u003e state with no signal observed for Fe\u003csup\u003e2+\u003c/sup\u003e (Kruanetr et al., 2018; Kumar et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Further, for Fe-S-PT; spectrum depicted the presence of Fe(2p), S (2p), Ti (2p), and O (1s) with Fe in Fe\u003csup\u003e3+\u003c/sup\u003e form and S as S\u003csup\u003e4+\u003c/sup\u003e ions.\u003c/p\u003e \u003cp\u003eThe atomic composition obtained for each catalyst is depicted in Table \u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and is found to be in good accordance with the composition acquired from EDX.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section3\"\u003e \u003ch2\u003e3.1.2 Optical Properties\u003c/h2\u003e \u003cdiv id=\"Sec18\" class=\"Section4\"\u003e \u003ch2\u003e3.1.2.1 UV-DRS\u003c/h2\u003e \u003cp\u003eImpact of doping on optical properties of nanomaterials was investigated using UV-DRS since optical activity is found to influence the photoactivity (Keerthana et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). The absorption response for all the materials was evaluated and is portrayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e from which it could be stated that in comparison to PT, addition of impurity resulted in a shift in absorbance for all the doped catalysts to a higher wavelength in visible region. Additionally, the band gap energies of all the catalysts were deduced using tauc plot as delineated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e. (αhν)\u003csup\u003e2\u003c/sup\u003e vs energy curve was extrapolated to determine the band gap energy (E\u003csub\u003eg\u003c/sub\u003e) for all the catalysts and a significant decrease in E\u003csub\u003eg\u003c/sub\u003e of PT with the introduction of foreign species could be seen which in turn justifies the proper dispersion of metal/non-metal impurities into PT (Garg et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Nakhate et al., \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). The band gap values are listed in Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e where the Eg of PT was reduced from 3.24 eV up to 2.431 eV in case of Fe-S-PT. This reduction in band gap with doping facilitates the utilization of synthesized nanomaterials under sunlight.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec19\" class=\"Section4\"\u003e \u003ch2\u003e3.1.2.2 Photoluminescence (PL) Spectra\u003c/h2\u003e \u003cp\u003eSeparation between the charge carriers and their recombination rate for all the fabricated materials was examined using PL analysis. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e, a strong peak around 320 nm can be observed for all the materials which arise due to the recombination process of conduction band-valence band charge carriers however, a significant decline in peak intensities with the introduction of foreign species into TiO\u003csub\u003e2\u003c/sub\u003e is visible from the spectrum with the peak almost evanescing for Fe-S-PT (Dong et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). PL is a surface phenomenon that is indicative of recombination rate where high peak intensity corresponds to high recombination rate and thus providing a shorter life span to the generated electron-hole pair (Keerthana et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Zangeneh et al., \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Significant reduction in the peaks with doping suggests that mixing of foreign species into TiO\u003csub\u003e2\u003c/sub\u003e can suppress the recombination of charge carriers and thus augment the separation between the carriers where Fe-S-PT with an almost flat peak delineate the most effective charge transfer to the target.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec20\" class=\"Section3\"\u003e \u003ch2\u003e3.1.3 Photoelectrochemical Performance\u003c/h2\u003e \u003cp\u003eEIS analysis was performed to evaluate the photoelectrochemical performance of the synthesized nanomaterials by comprehending their charge transfer activity. The radius of the arc depicts the charge transfer capability where small the radius corresponds to lower transfer resistance of electrons at the surface resulting in a higher transfer of charge (Angela et al., \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Wang et al., \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). It can be seen from Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e that with doping the arc radius showed a significant dwindle with minimum radius observed for Fe-S-PT. This denotes that Fe and S act as electron and hole acceptors respectively which aid in promoting the separation of electro-hole pairs thus providing an effective pathway to charge transfer (Li (a) et al., 2021). The obtained results are following the observation made in the PL study.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec21\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Photocatalytic Assessment\u003c/h2\u003e \u003cdiv id=\"Sec22\" class=\"Section3\"\u003e \u003ch2\u003e3.2.1 Preliminary Level Analysis\u003c/h2\u003e \u003cp\u003ePrior to the investigation of ability of synthesized materials to act as a photocatalyst, preliminary studies evaluating adsorption and photolytic behaviour in the presence and absence of UV light using PT as the catalyst was performed. All the experiments were carried out for 180 mins using 25 ppm PQ at natural pH of 6.3 under varied conditions unless stated otherwise. As validated from Fig. S2, both adsorption and photolysis resulted in minimal removal of 10% and 13% respectively. Moreover, the results revealed that with the introduction of UV light along with the catalyst, a sharp increase in the degradation percentage was achieved which however, decreased from 75\u0026ndash;66% with sunlight. This observation can be associated with the high band gap energy of TiO\u003csub\u003e2\u003c/sub\u003e, making it active only under UV irradiation (Zangeneh et al., \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Thus, to attain maximum PQ degradation at minimal cost, modification of PT was carried out to make it solar active and various process parameters were optimized.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec23\" class=\"Section3\"\u003e \u003ch2\u003e3.2.2. Role of doping and dopant concentrations\u003c/h2\u003e \u003cp\u003eDoping of TiO\u003csub\u003e2\u003c/sub\u003e with metal and/or nonmetal creates intra band gap levels which facilitate the reduction of band gap energy allowing the catalyst to perform under sunlight. Thus, PT was incorporated with Fe, Ni (metals), S, and C (nonmetals) and their effect on removal of PQ was evaluated under sunlight by varying the dopant concertation from 1.00 wt% to 2.50% with catalyst loading of 1 g/L. The change in degradation as a function of dopant concertation for each catalyst is depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e from which it can be ascertained that optimum values for Fe-PT, S-PT, and C-PT were 1.50 wt% while for Ni-PT 2.00 wt% depicted maximum efficiency. For each catalyst, PQ removal was found to increase with the increase in the dopant concentration up to a certain value due to the successful doping resulting in a reduced band gap however, this increase was then followed by a decrement. The reduction could be acknowledged by the reduction of the active surface sites on the catalyst (Varma et al., \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Moreover, amongst all the photocatalysts, 1.5% S-PT lead to maximum PQ removal. This observation is fully supported by the various characterizations performed as it has the lowest band gap energy along with a high surface area and small crystallite size. Further, in comparison to other photocatalysts, S-PT had lower electron-hole recombination as confirmed by the PL spectra.\u003c/p\u003e \u003cp\u003eFrom the above analysis Fe came out as the optimum metal dopant while S was the optimum nonmetal dopant thus, further studies were performed for process optimization of 1.5% Fe-PT and 1.5% S-PT.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec24\" class=\"Section3\"\u003e \u003ch2\u003e3.2.3. Role of varying catalyst loading\u003c/h2\u003e \u003cp\u003eSince the aim of the work is to develop an economically viable process of water treatment, the catalyst loading was optimized to achieve maximum possible degradation with the minimum usage of the catalyst. Assessments were done with catalyst loading ranging from 1.0 g/L to 2.0 g/L with the trends displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e11\u003c/span\u003e. The PQ removal tendency increased till catalyst loading of 1.5 g/L and later declined which could be due to the turbidity enhancement of the solution hindering the light penetration into the solution. Also, high catalyst dosage could become the source of catalyst agglomeration leading to light scattering (Sraw et al., \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). The results depict 87% PQ degradation with 1.5% Fe-PT and 93% PQ removal by 1.5% S-PT.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec25\" class=\"Section3\"\u003e \u003ch2\u003e\u003cb\u003e3.2.4. Effect of initial solution pH\u003c/b\u003e\u003c/h2\u003e \u003cp\u003eIn order to get a deeper insight into the behaviour of the pollutant and photocatalyst, the effect of pH on degradation rate was evaluated. The pH was varied from acidic to a neutral range of 3\u0026ndash;7 for both the catalysts using acetate buffer or buffer capsules while keeping all other conditions at optimum. The obtained trends are given in Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e12\u003c/span\u003e where natural PQ pH of 6.3 was achieved as the optimum pH. The rate of pollutant removal from water strongly depends upon the pHzpc of the catalyst, pKa of the pollutant, and the interaction between the catalyst surface and the pollutant (Pourzad et al., \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). For a solution having a pH lower than pKa, the cationic form of pollutant dominates. Similarly, in the case of catalyst; pH greater than pHzpc results in a negatively charged surface of the catalyst and vice-versa (M\u0026rsquo;Bra et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). For the given system, pKa of PQ is around 9 resulting in cationic form as dominant while pHzpc of both Fe-PT and S-PT is lower than 6.3 providing a negatively charged catalyst surface (Birben et al., \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; M\u0026rsquo;Bra et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Moein et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). This justifies pH 6.3 as the optimum pH since at this pH phenomenon of attraction between catalyst and pollutant surface occurs and several other studies have reported pH in the range of 5.9\u0026ndash;6.5 as optimum (Pourzad et al., \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2020\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eVariation in rate of PQ degradation with change in calcination temperature is discussed in supplementary file section \u003cspan refid=\"Sec1\" class=\"InternalRef\"\u003e1\u003c/span\u003eS with Fig. S3.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec26\" class=\"Section3\"\u003e \u003ch2\u003e3.2.5 Activity of Metal-Nonmetal codoped TiO\u003csub\u003e2\u003c/sub\u003e\u003c/h2\u003e \u003cp\u003eOnce both Fe-PT (metal doped) and S-PT (nonmetal doped) proved their individual efficacy as a solar active photocatalyst towards PQ degradation, Fe-S-PT-a codoped catalyst-was synthesized having nanorod like structure with large surface area and minimum recombination rate (as inferred from various analytical processes) and its photocatalytic behaviour was elucidated by keeping all other conditions at optimum as evaluated earlier i.e., 1.5% Fe doped into 1.5% S-PT, 1.5 g/L catalyst loading, pH 6.3 and calcination temperature 450\u0026ordm;C. One can observe from Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e13\u003c/span\u003e that a significant enhancement of 10% in the rate of PQ degradation occurred from 87% with Fe-PT to 97% Fe-S-PT along with 30 mins of reduction in time which are attributed to the lowest electron-hole recombination rate of Fe-S-PT in contrast to Fe-PT or S-PT since lower recombination corresponds to a longer life span of charged species responsible for OH˙ generation which eventually carriers out the degradation process.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec27\" class=\"Section3\"\u003e \u003ch2\u003e3.2.6 Evaluation of In-Situ Hybrid Process\u003c/h2\u003e \u003cp\u003eAs discussed above in section \u003cspan refid=\"Sec26\" class=\"InternalRef\"\u003e3.2.5\u003c/span\u003e, co-doping of Fe and S into TiO\u003csub\u003e2\u003c/sub\u003e led to a significant increase in PQ degradation however, the process required a long period of around 3h which hampers its real-time application. For a process to be feasible at industrial scale, it must be cheap as well as less time-consuming. The implication of sunlight as the source of energy makes the process cheap however, efforts must be made toward reduction of process time. Henceforth, a hybrid process involving photocatalysis and photo-Fenton simultaneously was performed using Fe-S-PT where TiO\u003csub\u003e2\u003c/sub\u003e acts as the base for photocatalysis while Fe facilitates the photo-Fenton process in the presence of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e. The reaction was carried out under sunlight with 1.5 g/L of Fe-S-PT at pH 6.3 and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e 500 uL/L and a sharp 47% decrement in the time required for PQ removal was encountered as given by Fig.\u0026nbsp;\u003cspan refid=\"Fig14\" class=\"InternalRef\"\u003e14\u003c/span\u003e where instead of 150 mins, 80 mins were sufficient enough to degrade PQ.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThis observation is associated with the dual process taking place where Fe\u003csup\u003e3+\u003c/sup\u003e acts as the sink for the electrons generated at the conduction band of TiO\u003csub\u003e2\u003c/sub\u003e thus, preventing the electron-hole recombination and also generating OH˙ resulting in higher radical formation in comparison to the single photocatalysis process as explained below (Talwar et al., \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2019\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eTiO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;hν \u0026rarr; h\u003csup\u003e+\u003c/sup\u003e + e\u003csup\u003e\u0026minus;\u003c/sup\u003e (1)\u003c/p\u003e \u003cp\u003ee\u003csup\u003e\u0026minus;\u003c/sup\u003e + O\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;H\u003csub\u003e2\u003c/sub\u003eO \u0026rarr; H\u003csub\u003e2\u003c/sub\u003eO\u0026thinsp;+\u0026thinsp;OH˙ (2)\u003c/p\u003e \u003cp\u003eFe\u003csup\u003e3+\u003c/sup\u003e + e- + H\u003csub\u003e2\u003c/sub\u003eO \u0026rarr; Fe\u003csup\u003e2+\u003c/sup\u003e + H\u003csup\u003e+\u003c/sup\u003e + OH˙ (3)\u003c/p\u003e \u003cp\u003eFrom the above analysis, it can be summarised that the hybrid process of photocatalysis and photo-Fenton provides a practically feasible real-life solution to the havoc of water pollution.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec28\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Kinetic Study and Synergistic Effect\u003c/h2\u003e \u003cp\u003eTo carry out the kinetic study of Fe-S-PT as a photocatalyst as well as a dual catalyst; at first, the effect of initial PQ concentration on degradation was determined by varying the concentration from 5 ppm to 45 ppm since as per the Langmuir Hinshelwood Hougen Watson model (LHHW), the initial rate of degradation is a function of initial concentration (Sraw et al., \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). As inferred from Fig. S4, initial concentration and degradation depicted an inverse relationship which was expected.\u003c/p\u003e \u003cp\u003eOnce the effect of initial concentration over degradation was determined, the kinetics was evaluated by plotting 1/r˳ vs 1/C˳. The obtained trend for both photocatalysis and dual process depicts a straight line as given in Fig.\u0026nbsp;\u003cspan refid=\"Fig15\" class=\"InternalRef\"\u003e15\u003c/span\u003e which confirms the application of the LHHW model. The value of the rate constant (kr) for both processes was calculated as K\u003csub\u003ephotocatalysis\u003c/sub\u003e = 0.93 mg/Lmin and K\u003csub\u003ehybrid\u003c/sub\u003e = 2.24 mg/Lmin. As expected, the rate constant for the dual process came out to be greater than the individual photocatalysis process.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFurther, the synergy of dual process over the discrete photocatalytic process was quantified as per the given equation (Talwar et al., \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2019\u003c/span\u003e)-\u003c/p\u003e \u003cp\u003e% Synergy = {(K\u003csub\u003ehybrid\u003c/sub\u003e - K\u003csub\u003ephotocatalysis\u003c/sub\u003e) / K\u003csub\u003ehybrid\u003c/sub\u003e} * 100 (4)\u003c/p\u003e \u003cp\u003eFrom the above equation, an increase of 58% in the reaction rate with the dual process marks the feasibility of this process and is due to a twofold reason i.e., the formation of hydroxyl radical is taking place not just by one process but due to multiple processes resulting in their production in abundance and further the utilization of electrons in the dual process makes the recombination infrequent.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec29\" class=\"Section2\"\u003e \u003ch2\u003e3.4 Probable Mechanism\u003c/h2\u003e \u003cp\u003eThe trapping experiments performed are discussed using Fig S5. Based on trapping studies one can state the degradation mechanism for the catalyst will mainly be governed by the OH˙ and e\u003csup\u003e\u0026minus;\u003c/sup\u003e. Prior to designing of mechanism, the potential values of conduction and valence bands were calculated using the relation (Kumar et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2018\u003c/span\u003e)-\u003c/p\u003e \u003cp\u003eE\u003csub\u003eVB\u003c/sub\u003e = X \u0026ndash; E\u003csub\u003ee\u003c/sub\u003e + 0.5E\u003csub\u003eg\u003c/sub\u003e\u003c/p\u003e \u003cp\u003eE\u003csub\u003eCB\u003c/sub\u003e = E\u003csub\u003eVB\u003c/sub\u003e - E\u003csub\u003eg\u003c/sub\u003e\u003c/p\u003e \u003cp\u003ewhere;\u003c/p\u003e \u003cp\u003eE\u003csub\u003eVB\u003c/sub\u003e: Potential of the valence band\u003c/p\u003e \u003cp\u003eE\u003csub\u003eCB\u003c/sub\u003e: Potential of the conduction band\u003c/p\u003e \u003cp\u003eX: Electronegativity of TiO\u003csub\u003e2\u003c/sub\u003e (~\u0026thinsp;5.8 eV)\u003c/p\u003e \u003cp\u003eE\u003csub\u003ee\u003c/sub\u003e: Energy of electrons (~\u0026thinsp;4.5 eV)\u003c/p\u003e \u003cp\u003eE\u003csub\u003eg\u003c/sub\u003e: Band gap energy\u003c/p\u003e \u003cp\u003eThus, for PT E\u003csub\u003eVB\u003c/sub\u003e = 2.92 eV and E\u003csub\u003eCB\u003c/sub\u003e = -0.32 eV. Further, on doping of Fe (metal) into PT fermi levels of CB would shift towards a positive value while the energy of VB will remain unchanged giving E\u003csub\u003eVB\u003c/sub\u003e = 2.92 eV and E\u003csub\u003eCB\u003c/sub\u003e = 0.082 eV. Similarly, on adding S (nonmetal) to PT VB will shift to higher energy while the energy for CB will remain unchanged giving E\u003csub\u003eVB\u003c/sub\u003e = 2.288 eV and E\u003csub\u003eCB\u003c/sub\u003e = -0.32 eV (Kang et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2008\u003c/span\u003e). Henceforth; on co-doping of Fe and S, both CB and VB will shift with Fe (doped as Fe\u003csup\u003e3+\u003c/sup\u003e) acting as electron acceptor for generation of Fe\u003csup\u003e2+\u003c/sup\u003e and thus leading to the photo-Fenton process while at VB holes combine with water to generate OH˙ performing photocatalysis. This dual process of photocatalysis and photo-Fenton is outlined below by Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec30\" class=\"Section2\"\u003e \u003ch2\u003e3.5 Mineralization Study\u003c/h2\u003e \u003cp\u003eThe purpose of the study is not just the removal of PQ from water but also to break down this complex structure into a simpler, nontoxic product. This was ensured by the determination of C content reduced with time using TOC analysis. Figure\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e16\u003c/span\u003e illustrates the extent of mineralization undergone by PQ during degradation via a hybrid process of 25 ppm solution at pH 6.3 and 1.5 g/L of Fe-S-PT and was calculated to be 87% in 80 mins only.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAgainst this 87% TOC removal, literature has reported 27.45% TOC elimination of 10 ppm PQ via photocatalysis under UV illumination (M\u0026rsquo;Bra et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2019\u003c/span\u003e) and 50% for 150 ppm solution after 300 mins of UV irradiation (Moctezuma et al., \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2006\u003c/span\u003e). A detailed comparison of the present work with the literature is provided in Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e below.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eComparative Study for Degradation of PQ\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"8\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCatalyst\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eProcess\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eEnergy Source\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003epH\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eTime (mins)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003e% TOC\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003e% Degradation\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eReference\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1%Fe-1%Ti/SiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePhotocatalysis\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eSunlight\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e67\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e(Kruanetr \u0026amp; Wanchanthuek, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2018\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN-TiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePhotocatalysis\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eVisible\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e5.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e120\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e61.72\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e(Suwannaruang et al., \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2018\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBCBF\u003c/p\u003e \u003cp\u003eCBF\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePhotocatalysis\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eSunlight\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e7.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e120\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e84.5\u003c/p\u003e \u003cp\u003e52.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e(Kumar et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2018\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCe-TNTs\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePhotocatalysis\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eUV\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e240\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e51.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e80.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e(Eleburuike et al., \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2016\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe\u003csup\u003e2+\u003c/sup\u003e/H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eFenton\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eDark\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e240\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e(Santos et al., \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2011\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePhotocatalysis\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eUV\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e37.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e66.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e(Phuinthiang \u0026amp; Kajitvichyanukul, \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2019\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe\u003csup\u003e2+\u003c/sup\u003e/H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePhoto-Fenton\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eUV\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e64.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e(Trov\u0026oacute; et al., \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2013\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe-S-PT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHybrid\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eSunlight\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e6.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e87\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003eThis Study\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec31\" class=\"Section2\"\u003e \u003ch2\u003e3.6 Intermediates Formed\u003c/h2\u003e \u003cp\u003eApart from mineralization studies, breaking down of PQ into simpler compounds via hyrid process was further justified by performing the LCMS of the solution at various time intervals and the obtained peaks are given in Fig S6. The major characteristics peak for untreated PQ were observed at m/z 144 (4%), 171 (100%), 185 (80%) and 186 (50%) where m/z\u0026thinsp;=\u0026thinsp;186 corresponds to cationic paraquat without chloride ions while demthylation from cationic paraquat results into the ion fragment of m/z\u0026thinsp;=\u0026thinsp;171 (Flor\u0026ecirc;ncio et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2004\u003c/span\u003e; Marien et al., \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Moreover, the fragmentation of m/z\u0026thinsp;=\u0026thinsp;186 gives m/z\u0026thinsp;=\u0026thinsp;185 monocation fragment which on loss of -CH\u003csub\u003e3\u003c/sub\u003eCN yields m/z\u0026thinsp;=\u0026thinsp;144 (Evans et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2001\u003c/span\u003e; Flor\u0026ecirc;ncio et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2004\u003c/span\u003e). After performing hyrid process for 30 mins, multiple peaks indicative of PQ breakdown was observed at m/z\u0026thinsp;=\u0026thinsp;216 (2%), 201 (7%), 172 (10%), 170 (3%), and 158 (10%) apart from prior obtained peaks at 171 (100%), 185 (29%) and 186 (8%) (Evans et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2001\u003c/span\u003e; Flor\u0026ecirc;ncio et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2004\u003c/span\u003e; Marien et al., \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Further, after 55 mins almost all of the above obtained peaks disappeared with only m/z\u0026thinsp;=\u0026thinsp;94 (15%), 158 (8%), 185 (5%) and 216 (27%) remaining. Formation and removal of major peaks confirms these species to be intermediates during the process. Furthermore, disappearance of the peaks associated with PQ (m/z\u0026thinsp;=\u0026thinsp;144, 171, 186) or decline in their peak intensity (m/z\u0026thinsp;=\u0026thinsp;185) marks the removal of PQ from the solution while increase in the intensity for m/z\u0026thinsp;=\u0026thinsp;216 shows the formation of new product i.e. dipyridone which is less toxic than PQ (Cartaxo et al., \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). Finally at the end of the process, m/z\u0026thinsp;=\u0026thinsp;94 (8%) and 216 (16%) were only present depicting degradation of complex PQ into simpler and less toxic species which are better for the environment. The probable degradation pathway of PQ is depicted in scheme \u003cspan refid=\"Sch2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn this study, PT along with metal and nonmetal modified TiO\u003csub\u003e2\u003c/sub\u003e was synthesized using hydrothermal treatment and employed for degradation of PQ under UV and sunlight. Investigation of their optical and morphological properties indicated that with the introduction of metal or nonmetal in TiO\u003csub\u003e2\u003c/sub\u003e lattice enhancement in its properties occurred with S-PT depicting lowest and gap energy, high surface area and growth of nanorods. Moreover, this 1.5%S-PT performed as an excellent photocatalyst resulting in 93% PQ removal followed by 1.5%Fe-PT degrading 87% PQ. However, with aim of reducing reaction time and attaining a higher degradation rate, Fe-S-PT codoped catalyst was prepared and a dual process of simultaneous photocatalysis and photo-Fenton was carried out. A sharp decrement of 47% in the process time was attained with this hybrid process along with synergy of 71%. The trapping experiments declared OH˙ and e\u003csup\u003e\u0026minus;\u003c/sup\u003e as the active species based on which the degradation mechanism was designed. Mineralization of 87% in 80 mins indicated the conversion of complex PQ into simpler and non-toxic forms which was further proved by the LCMS investigating various intermediates formed. The present study overall has the economical real-time application of degrading PQ within 80 mins utilizing freely available sunlight at the benign pH of 6.3.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eYamini Pandey would like to thank Jawaharlal Nehru Memorial Fund, New Delhi for providing scholarship to carry out research work. All the authors also acknowledge TEQIP-III (Dr. SSB UICET, Panjab University, Chandigarh) for giving financial assistance during this work. We also recognize Central Instrumentation Facility (CIL) and SAIF, Panjab University for performing various characterization and analytical analyses.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors Contributions\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eYamini Pandey:\u003c/strong\u003e Data curation, Formal analysis, Investigation, Writing \u0026ndash; original draft, preparation. \u003cstrong\u003eAarsee Dhindsa:\u003c/strong\u003e Reviewing.\u003cstrong\u003e\u0026nbsp;Anoop Verma:\u003c/strong\u003e Supervision, Methodology, Reviewing. \u003cstrong\u003eAmrit Pal Toor:\u003c/strong\u003e Visualization, Conceptualization, Supervision, Validation.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting Interests\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eAll authors hereby declare that they do not have any competing financial or personal interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData and Code Availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupplementary Information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSupplementary data file attached separately.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthical Approval\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis is inapplicable \u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to Participate\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis is inapplicable\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to Publish\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe manuscript may be published by the journal with the approval of all authors.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis research receives no external funding.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAvailability of data and materials\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll the necessary data has been provided in the manuscript; any additional data required may be provided on demand.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eALOthman, Z. 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Photomineralization of recalcitrant wastewaters by a novel magnetically recyclable boron doped-TiO\u003csub\u003e2\u003c/sub\u003e-SiO\u003csub\u003e2\u003c/sub\u003e cobalt ferrite nanocomposite as a visible-driven heterogeneous photocatalyst. Journal of environmental chemical engineering, 6(5), 6370-6381.\u003c/li\u003e\n\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":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Photocatalysis, Photo-Fenton, Synergy, Paraquat, co-Doped TiO2","lastPublishedDoi":"10.21203/rs.3.rs-3909915/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3909915/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003ePresence of non-biodegradable organic compounds, mainly pesticides in water bodies peril humans as well as aquatic life. Paraquat (PQ) is one such widely used Class II herbicide associated with Parkinson\u0026rsquo;s disease. Herein, pristine TiO\u003csub\u003e2\u003c/sub\u003e (PT), as well as metal (Fe-PT, Ni-PT) and nonmetal (C-PT, S-PT), modified TiO\u003csub\u003e2\u003c/sub\u003e was synthesized using hydrothermal treatment for mineralization and degradation of PQ. The crystallite size from XRD exhibited the prepared catalysts to be nanomaterials while FESEM confirmed the nanorod formation. Moreover, morphological analysis established the occurrence of doping in PT. Through optical properties, reduction in band gap from 3.2 eV to 2.4 eV was found which was accompanied by decrease in electron-hole recombination rate. Further, nanocomposites were investigated for PQ removal with S-PT depicting 93% degradation under solar radiations followed by Fe-PT degrading 87% PQ indicating that with optimum doping levels and proper reduction of band gap, TiO\u003csub\u003e2\u003c/sub\u003e can be made more enthusiastic towards degradation and remediation process. Further, hybrid process employing photocatalysis and photo-Fenton simultaneously was utilised by synthesising Fe-S-PT, a codoped catalyst. This codoped Fe-S-PT resulted in a sharp decrement of 47% in processing time which is attributed to the presence of OH˙ and e\u003csup\u003e\u0026minus;\u003c/sup\u003e. Moreover, a degradation mechanism for Fe-S-PT was proposed along with the evaluation of extent of mineralization taking place. Lately, intermediates formed during the process were identified. Overall, study is extremely significant towards providing a practical and economical solution for PQ degradation using hybrid process within 80 mins at the benign pH of 6.3.\u003c/p\u003e","manuscriptTitle":"Elucidating Synergistic Effect of In-Situ Hybrid Process Towards Paraquat Abatement","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-02-02 06:17:52","doi":"10.21203/rs.3.rs-3909915/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"e9be7d8b-21f9-4358-a605-fee894b47279","owner":[],"postedDate":"February 2nd, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-02-17T15:29:30+00:00","versionOfRecord":[],"versionCreatedAt":"2024-02-02 06:17:52","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-3909915","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3909915","identity":"rs-3909915","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}