{"paper_id":"3eb68f12-85fd-4a6d-a6c5-a61d2037f11c","body_text":"Sorption-photocatalysis of structurally distinct pesticides using polythiophene/TiO2 composites: Kinetics, equilibrium, reusability and operational economics | 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 Sorption-photocatalysis of structurally distinct pesticides using polythiophene/TiO2 composites: Kinetics, equilibrium, reusability and operational economics Pareshkumar Moradeeya, Anil Kumar Madhava, Archana Sharma, Shaik Basha This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-1839933/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 An integrated process involving adsorption and photocatalysis are utilized for the breakdown of three different pesticides such as 2,4-D, 4-CPA and TCP. Photo-catalysts were fabricated using polythiophene supported TiO 2 composites and utilized for the pesticides degradation under UV light irradiation. The synthesized materials were characterized for elemental, microscopic, spectroscopic and spectrophotometric properties. The outcome shows that polythiophene supported titanium dioxide systems can successfully facilitate the breakdown of pesticides under UV irradiation. The photocatalytic effectiveness of the TiO 2 catalyst was significantly improved by the addition of polythiophene. Maximum amount of adsorption capacity for 2,4-D, 4-CPA and TCP were 8.18, 6.333, and 9.681 mg/g by pTh-1. The modified version of the Langmuir-Hinshelwood (L-H) model explained the inter-relationship between the adsorption and photodegradation. Results explained that the pTh-1 catalyzed photodegradation of 4-CPA, TCP and 2,4-D exists the surface reaction which was rate-limiting. Langmuir- Hinshelwood and electrical energy per order (E EO ) model provided good fit with batch-mode experiments. Furthermore, these models were successful in elucidating the mechanisms of photocatalytic degradation when pTh-1 was available in the reaction mixture. Degradation 2 4-dichlorophenoxyacetic acid Triclopyr acid Polythiophene TiO2 4-Chlorophenoxyacetic acid Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1. Introduction The availability of pure and wholesome water is both a significant concern for human life. However, sewage and industrial effluent that is dumped into the environment degrade fresh drinking water, making it impossible to provide clean water to residents and ecosystems in the surrounding area (Mohamed et al., 2018). Various types and amounts of water contaminants, organic compound (dyes, pesticides, pharmaceutical residual, and petrochemicals-hydrocarbon), inorganic compounds (heavy metals, ammonia, phosphates and chemical fertilizers) commonly found in discharged wastewater (Moradeeya et al., 2022a; Mohamed et al., 2018). Water contamination by synthetic pesticides is one of the most serious issues confronting environmental protection measures (Lam et al., 2018). Herbicides are poisonous organic compounds with a limited biodegradability that are responsible for a variety of environmental issues such as aesthetic loss, high pollution load, eutrophication, and aquatic system disturbances (Nitschke et al., 1999; Shelton and Miller, 2002). Pesticides contaminate the aquatic environment in a variety of ways, including runoff, leaching, and spray drift, all of which pose substantial health concerns to both the terrestrial and aquatic ecosystems. All layers of biological organization, including primary producers, microbes, invertebrates and fishes, are immediately affected by this exposure. Furthermore, chlorinated organic compounds, as contaminants in available water sources, can cause the water's health to deteriorate and has been linked to increased risk of cancer and mutations in humans as well as wildlife (Carpenter, 2011; Ashraf, 2017). In order to mitigate the damage that herbicides and other contaminants might do, a few different approaches have been tried to remove them from water supplies. There are a variety of methods that can be applied, including adsorption, coagulation, flocculation, advanced oxidation, and bioremediation (Moradeeya et al., 2022a). Herbicide adsorption removal is easy and involve low-maintenance and the amount of sludge produced is less than with other procedures (Moradeeya et al., 2017). It was also suggested that advanced oxidation of herbicides would be an effective strategy, however the combined adsorption photocatalysis method is more promising in terms of cost and toxicity reduction (Sheng et al., 2019; Chang et al., 2020; Fazal, et al., 2020;). Straightforward photolysis of oxidants such as hydrogen peroxide or ozone under the influence of UV illumination, homogeneous (Fenton and photo-Fenton) and heterogeneous photocatalytic degradation are the technique for removing pesticides (Moradeeya et al., 2022b; Alalm et al., 2015; Zanoni et al., 2022). Titanium dioxide (TiO 2 ) is a commonly used photocatalyst and the most significant disadvantage is the difficulty to remove them from solution. TiO 2 particle adhesion to particular surfaces has been suggested as a solution to the problem of photocatalyst removal from reaction media (Ong et al., 2014; Perović, et al., 2020; Wang et al., 2020). Nanostructured polymers with adsorption and photocatalytic characteristics have attracted a lot of attention in the field of water treatment (Riaz et al., 2015; El-Bery et al., 2021). With the aforementioned problem, the presented research aims to fabricate polythiohene (pTh) coated TiO 2 nanocomposites and to evaluate their efficacies in removing three structurally distinct chlorinated phenoxyacetic acid (herbicides) from aqueous solutions. Thus, our work seeks to construct nanopolymer polythiophene on the surface of the titanium dioxide using an in-situ polymerization technique to create (pTh-TiO 2 ) for the adsorption and photocatalytic removal of acidic herbicides from water. To perform photolysis using the fabricated nanocomposites under ultraviolet (UV) light as a function of catalyst stability, herbicide’s concentrations, illumination time, solution pH, catalyst dose, and role of the combination process. To elucidate the pesticides removal mechanism using kinetic and equilibrium models. 2. Experimental 2.1. Materials 4-chlorophenoxyacetic acid (4-CPA) and 2,4-Dichlorophenoxyacetic acid (2,4-D) were purchased from Otto Chemical, (India) while Triclopyr Acid (TCP) was kindly given by Aimco Pesticides (India). Thiophene was procured from Sigma Aldrich while HCl, chloroform and NaOH were products of Qualigens (India). Water HPLC grade and methanol were used for the chromatographic analytical tests and non-sterile Millex® syringe filters (0.45 µm) were used in this study. A methanol/water mix system was used to make the pesticide standard stocks, which were then diluted in distilled water to make the final concentrations. 2.2. Preparation and characterization of coated nanocomposites pTh-TiO 2 nano-composites were fabricated using the method described by Cao et al. (2020) with slightly modification. Varying amount of TiO 2 (1.6, 3.2 and 4.8 g) and 20 mL of chloroform was mixed in an ultrasonic bath for 15 min. To this mixture, 0.21 mL of thiophene was added and stirred for 30 min; further FeCl 3 solution (5 g in 60 mL chloroform) was added drop wise in the TiO 2 /thiophene solution, which was placed for a further 24 h under stirring under cooling in an ice bath. After 24 h, the reaction mixture was filtered to collect the black-reddish precipitate, which was washed with distilled water once, followed by alternate wash with methanol, 1.0 N HCl. The washing was repeated until filtrate become colorless, and nonreactive, then placed in an oven at 70°C for 24 h for drying. Resultant materials were designated as pTh-1, pTh-2 and pTh-3. The fabricated materials were characterized using different analytical instrumentation as described in the Supplementary Materials Experimental S1&S2. 2.3. Batch sorption tests The photocatalytic activity of pTh-TiO 2 was examined for herbicide degradation using UV light irradiation from a high-pressure mercury lamp (365 nm light). Adsorption and photocatalysis experiments were conducted at room temperature in a borosilicate glass photochemical reactor with an immersion well. For a period of thirty minutes, adsorption studies were carried out in utter darkness before photodegradation tests were performed in order to ascertain the extent to which adsorption contributed to the overall removal rate of pesticides. Subsequently attaining adsorption equilibrium, pesticides with pTh-TiO 2 mixtures were exposed to UV light for photocatalytic destruction. The screening assays used 1.0 g/L of pTh (pTh-1, pTh-2 and pTh-3) with fixed pesticide concentration of 10 mg/L. Aliquots were withdrawn at various time interval, filtered and estimated the removal percentage. 2.4. Effect of process parameters on removal efficiencies The effect of process parameters such as catalyst dose, pH value, irradiation time and initial herbicides concentrations on sorption-photocatalysis were evaluated using one-factor-at-a-time approach. The varying concentrations of the catalyst (0.5–1.5 g/L), pH (4.3–10.8) and individual herbicides concentrations (10–25 mg/L) in 50 mL of the reaction volume. The batch reactions were agitated at 150 rpm and residual concentrations were estimated at different time (30 min for adsorption and 120 min for photodegradation). 2.5. Equilibrium studies The adsorption equilibrium of by the pTh-TiO 2 nanocomposites were investigated to understand the adsorption mechanism and the proficiency of the fabricated nanocomposites. For this purpose, 1.0 g/L pTh-TiO 2 nanocomposites was agitated with 50 mL of 2,4-D, 4-CPA and TCP solutions (10–25 mg/L) individually for 30 min. The residual concentrations of the pesticides were quantitatively assessed using high performance liquid chromatography (HPLC) and the observed equilibrium uptake were fitted to the different isotherm models viz. , Langmuir, Freundlich, Redlich-Peterson and Sips. 2.6. Kinetics studies The effect of contact duration on herbicides (2,4-D, 4-CPA and TCP) adsorption by pTh-TiO 2 was examined by shaking 1.0 g/L of pTh-TiO 2 with 50 mL of 10–25 mg/L individual herbicide solution under restricted light source for 30 min. Aliquots were withdrawn to assess the residual concentrations of 2,4-D, 4-CPA and TCP. The observed data were fitted to different kinetic and isotherm models to describe the adsorption behavior of pTh-TiO 2 nanocomposites. Langmuir-Hinshelwood rate determines the interrelationship between the initial degradation and concentration of the pollutants (Krishnakumar and Swaminathan, 2011). $$\\frac{1}{{k}_{app}}=\\frac{1}{{k}_{c }{K}_{LH}}+\\frac{{C}_{0}}{{k}_{c}}$$ 1 where C 0 is the initial concentration (mg/L) of the pollutant, K LH is the Langmuir-Hinshelwood adsorption equilibrium constant (mg/L) whereas k c is rate constant (mg/L/min). 2.7. Evaluation of catalyst’s stability One of the most important requirements for commercial use of a synthetic catalyst is its stability and reusability for several cycles of herbicide removal. Stirring 1.0 g/L of pTh-1 with 50 mL of individual herbicide solutions (10 mg/L) for five cycles was used to examine this. The composite powder was rinsed with distilled water, methanol and diluted HCl after each cycle and dried at 70°C for 180 min before being utilized in the following cycle. 3. Results And Discussion 3.1. Synthesis and characterization of pTh-TiO 2 nanocomposites Diffraction patterns of TiO 2 and pTh-TiO 2 (Supplementary Materials Figure S1) shows the crystalline nature of anatase TiO 2 (Mahlake et al., 2019). The major peaks are located at crystal planes (101), (004), (200), (105), (211) and (204) which is consistent with the applicable standard reference (Li et al., 2014). XRD pattern of pTh-1 shows almost identical strong diffraction peaks at the corresponding position of pure TiO 2 in polythiophene matrix. Simultaneously, no new diffraction peaks appeared in the pattern of the synthesized composites, probably due to the low polythiophene content of the composites (Xu et al., 2010; Chen et al., 2018). However, the presence of polythiophene, the diffraction peak strength fell marginally implying the negligible effect of polythiophene on TiO 2 coating. The morphology of TiO 2 and pTh-1 was studied using FE-SEM, with images acquired at 5 KX and 100KX magnifications, as shown in the Supplementary Materials Figure S2. Images show that the TiO 2 are homogeneous and seem to be agglomerated. The composite’s surface activity increased due to the high surface-to-volume ratio, resulting in a greater degree of UV light absorption. Polythiophene distribution across TiO 2 is consistent, implying that the pTh-1 composite is made up of granular complexes. Because of the loose and porous character of pTh-1 resulting in overall roughness, its adsorption and/or photocatalysis efficacy is greatly boosted. To demonstrate the typical peaks of the products, IR spectra of pure TiO 2 and pTh-1 samples were examined, and the findings are shown in Supplementary Materials Figure S3. FT-IR spectra of TiO 2 had three major absorption peaks can be recognized between 3435 and 1630 cm − 1 due to OH groups (Zhang et al., 2019; Praveen et al., 2014). Some of the distinctive peaks given to pTh are faint in the composite, possibly due to overlap with strong peaks ascribed to TiO 2 . Furthermore, due to the impact of OH, the loading rate of pTh may be decreased when the reaction is carried out in aqueous medium (Chen et al., 2018; Roncali, 1992). Peaks at 695 and 784 cm − 1 are often attributed to the C–H out-of-plane deformation (Shoubin et al., 2011). C-S bond, which is the presence of thiophene monomer in the polymer backbone, corresponds to the absorption of 697 cm − 1 (Martinez et al., 2000). A stretching vibration of C-C bonds is most likely responsible for the band about 1350 cm − 1 . In polythiophene, the stretching frequency of the C = C bond is between 1443 and 1523 cm − 1 . Several faint peaks in the 2800–3100 cm − 1 and 1690 cm − 1 ranges can be ascribed to C–H and C = C characteristic peaks, respectively (Shoubin et al., 2011). It's worth noting that the peaks at 1676 cm − 1 in the spectra of pTh might potentially be attributed to C = O (Chen et al., 2018). UV-vis spectra of pure TiO 2 and pTh-1 Fig. 1 a showed strong ultraviolet (UV) absorption with a peak and the visible range (In pTh-1). Photo-generation by TiO 2 is linked to a significant signal focused in the UV zone in the spectrum of pTh-1 nanocomposite, where a notable peak is detected around the visible zone, which is related with the π→π* electronic transitions of delocalized pi-bonds (Ansari et al., 2015). The absorption peak at 700 nm has vanished, but there is a noticeable rise in absorption between UV and visible region (Xu et al., 2010). Because of the polythiophene coating on the surface of TiO 2 , the UV area moves toward the region of visible wavelength. pTh-1’s absorption peak has a red shift, indicating that it is a promising candidate for organic pollutant degradation when exposed to UV, visible, and solar radiation. According to Tauc’s plot (Fig. 1 b), the band-gap energies for pure TiO 2 and pTh-1 were 3.2 and 1.9 eV, respectively. The photo-induced charge transfer from polythiophene to TiO 2 can be accelerated by this interaction (Zia et al., 2021). As a result of the polythiophene coating on TiO 2 , the photocatalytic effectiveness was improved. 3.2. Screening of composites The screening of nanocomposites was carried out to evaluate the most optimal weight ratio of TiO 2 in the synthesis during the fabrication of pTh-TiO 2 . The photocatalytic degradation efficiencies of pTh-1, pTh-2, PTh-3 and unaltered TiO 2 under UV light are illustrated in the Fig. 2 . The adsorption efficiency of pTh composites were arranged in the order of better efficacies: pTh-1 > pTh-2 > pTh-3 > TiO 2 . As a result, pTh-1 was chosen for future inquiry, and the activities of the nanocomposites were clearly higher than bare TiO 2 after adsorption-desorption equilibrium and irradiation. Reaction sets showed strong adsorption within 30 min, which is consistent with the findings, which explained why the nanocomposite outperformed the naked TiO 2 . The surface modification of TiO 2 with polythiophene improves the photo-response of the pTh-1 nanocomposites. 3.3. Effect of process variables on sorption-photocatalysis Aqueous reaction mixtures containing the individual pesticides as well as the pTh-1 are influenced by solution’s pH. Effect of initial pH on the sorption capacity of composite was explored in pH 4.3–10.8 for better elucidation. Acidic pH levels are more favorable for selected three herbicides in adsorption (data not shown), similar trend observed by others (Palma et al., 2015; Nematollahzadeh et al., 2021). Protonation-deprotonation of composite functional groups are affected by pH fluctuations. Sorption was significantly facilitated by the acidic environment, and surface functionalization was encouraged by the decreased pH of the solution throughout the contacting process. On the polymer chain, an electrostatic potential distribution is formed, and the sites with defect states become adsorption active (Moradeeya et al., 2022b; Nematollahzadeh et al., 2021). It was observed that the sorption-photocatalytic activity of the pTh-1 was reduced when the solution’s pH increased, and the catalyst showed the highest level of efficacy at an acidic pH as shown in Fig. 3 . An important factor in the formation of the pTh-1's net surface charge is its protonation and deprotonation at acidic and basic pH levels. The effect of the dose of pTh-1 (0.5–1.5 g/L) on the photodegradation of 2,4-D, 4-CPA and TCP was tested using a constant concentration of the aforementioned pesticides (10 mg/L) at the ideal pH over a length of time of 120 min. The findings are presented in Fig. 4 , which illustrates a comparison of the entire reaction involving adsorption and photocatalysis increases, whereas photo-degradation efficiency declines, with rise in the catalyst dosage. Aggregation of the photocatalyst, which leads to a smaller available surface area on the photocatalyst for photon absorption, may have contributed to a decrease in the effectiveness of the degradation process when a high dose was used (Malato et al., 2009). Initially, the rate of adsorption is faster due to available number of active site and splitting effect of the flux between pTh-1 and the tested pesticides. Initial pesticide concentration influences the kinetic rate constant, which decreases with increasing initial pesticide concentration (Moradeeya et al., 2022b). The tests on the decomposition of pesticides by UV irradiation follow the pseudo-first order kinetics with regard to the concentration of pesticides in the solution phase. $$\\text{r}=-\\frac{d\\text{C}}{dt}=\\frac{{\\text{K}}_{\\text{a}\\text{d}\\text{s}}{k}_{\\text{L}-\\text{H}}\\text{C}}{1+{\\text{K}}_{\\text{a}\\text{d}\\text{s}}\\text{C}}$$ 2 $$\\text{r}=-\\frac{d\\text{C}}{dt}={\\text{K}}_{\\text{a}\\text{d}\\text{s}}{k}_{\\text{L}-\\text{H}}\\text{C}={k}_{app}\\text{C}$$ 3 Applying the limits of C = C 0 at t = 0 with C 0 being the starting concentration in the solution phase and t being the reaction time; $$ln\\left(\\frac{{C}_{0}}{{C}_{t}}\\right)={k}_{app}t$$ 4 where, k app is the apparent rate constant influenced by the pesticide’s concentration. Figure 5 depicts a plot of the natural logarithm of the concentration ratio C 0 /C against time for all of the trials that were conducted with various initial bulk concentrations of pesticides. The values of k app can be derived in an easy and straightforward manner by performing a linear regression as given in the Table 1 . Plot of 1/k app versus C 0 exhibits a linear variation, so validating the Langmuir-Hinshelwood relationship as a description of the initial rates of breakdown. The values of K R and K L−H , which were determined separately from the plots. Table 1 Rate constants for the photocatalytic degradation of (a) 2,4-D, (b) 4-CPA and (c) TCP removal by pTh-1 Parameter Effect of concentration for TCP Concentration (mg/ L) 10 15 20 25 k app (1/min) 0.004 0.003 0.002 0.002 RSS 0.005 5.97E-04 7.89E-04 0.001 Pearson's r 0.997 0.999 0.999 0.997 R-Square (COD) 0.994 0.999 0.998 0.994 Adj. R-Square 0.993 0.998 0.997 0.993 E EO experimental 870400 1160533 1740800 1740800 k LH (mg/ L/ min) 0.084 K R (L/mg) 0.068 Effect of concentration for 2,4-D Concentration (mg/ L) 10 15 20 25 k app (1/min) 0.010 0.009 0.008 0.007 RSS 0.055 0.025 0.010 0.014 Pearson's r 0.994 0.996 0.998 0.997 R-Square (COD) 0.989 0.993 0.996 0.994 Adj. R-Square 0.987 0.993 0.996 0.993 E EO experimental 34816 386844 435200 497371 k LH (mg/L/ min) 0.302 K R (L/mg) 0.043 Effect of concentration for 4-CPA Concentration (mg/L) 10 15 20 25 k app (1/min) 0.015 0.012 0.010 0.009 RSS 0.027 0.009 0.015 0.013 Pearson's r 0.998 0.999 0.998 0.998 R-Square (COD) 0.997 0.998 0.997 0.996 Adj. R-Square 0.997 0.998 0.996 0.996 E EO experimental 23211 29013 34816 38684 k LH (mg/L/ min) 0.284 K R (L/mg) 0.079 3.4. Equilibrium studies Langmuir theory states that the adsorption proceeds in a single layer on the surface of adsorbents with homogeneous active sites scattered across its entire surface. An increase in absorption capacity produces an exponential decrease in surface binding energy, generating multilayers from adsorbed ions, according to the Freundlich model (Wang and Guo, 2020). Redlich-Peterson and Sips models are hybrid model of Langmuir and Freundlich models widely used in homogeneous and heterogeneous sorption tests (Wang and Guo, 2020). The fitting of equilibrium experimental data with isotherms for the tested pesticides are shown in Fig. 6 and model parametric values are given in the Table 2 . It was noted that the Sips isotherm is followed by equilibrium data for chosen herbicides by the pTh-1 nanocomposites. Table 2 Equilibrium isotherm constants for (a) 2,4-D, (b) 4-CPA and (c) TCP removal by pTh-1 Isotherms Parameters TCP 2,4-D 4-CPA Langmuir Q max (mg/g) 11.738 9.250 7.067 K L (L/mg) 0.266 0.393 0.284 R L 0.285 0.219 0.277 Reduced Chi-Sqr 0.366 0.082 0.018 R-Square (COD) 0.979 0.993 0.997 Adj. R-Square 0.974 0.991 0.996 RSS 1.466 0.331 0.072 Freundlich K F (L/mg) 4.349 4.197 2.600 n 3.619 4.387 3.539 Reduced Chi-Sqr 0.775 0.265 0.123 R-Square (COD) 0.957 0.978 0.981 Adj. R-Square 0.946 0.973 0.977 RSS 3.101 1.062 0.493 Redlich-Peterson K RP (L/ mg) 1.662 2.387 1.468 a RP (L/ mg) 0.020 0.131 0.113 β 1.606 1.208 1.184 Reduced Chi-Sqr 0.069 0.044 0.001 R-Square (COD) 0.997 0.997 0.999 Adj. R-Square 0.995 0.995 0.999 RSS 0.209 0.132 0.003 Sips Q max (mg/ g) 9.681 8.180 6.333 B (L/ mg) 0.277 0.383 0.321 n 2.700 1.986 1.472 Reduced Chi-Sqr 0.015 0.024 5.50E-05 R-Square (COD) 0.999 0.998 0.999 Adj. R-Square 0.998 0.997 0.999 RSS 0.045 0.072 1.65E-04 3.5. Kinetic studies Pseudo-first, pseudo-second, Elovich and intraparticle diffusion models were used to fit the experimental data in order to make a prediction about the removal mechanism (Zhou et al., 2011; Edet and Ifelebuegu, 2020; Yuan et al., 2015). Intra-particle diffusion is another kinetic model used to study the rate of pesticides adsorption on pTh-1 (data not shown). The plots had two separate regions where the first linear trend which indicates external diffusion of pesticides by active sites, spread over the pTh-1’s surface. Each of these regions are represented by the first linear trend. The second linear component represents the intra-particle diffusion by active sites dispersed on the pTh-1 and eventually the development of the equilibrium. Intra-particle diffusion constant, k id values were obtained from the slope of the second linear portions of the plot of qt versus t 0.5 for various pesticides concentrations. As can be shown in Fig. 7 , a pseudo-second order kinetic model that provides an appropriate description of the sorption kinetics of both of the targeted pollutants onto pTh-1 is supported by values of R 2 that are high and RSS values that are low. In addition, there is only a slight variation between the calculated and experimental values of q e , which further supports the validity of the pseudo-second order model that is presented in Tables 3 and 4 . A similar observation was reported in a polythiophene-based composite for the adsorption of heavy metals (Arabahmadi and Ghorbani, 2017). Table 3 Estimated parametric values of pseudo-first and pseudo-second order models Model Parameters TCP (mg/L) 2,4-D (mg/L) 4-CPA (mg/L) 10 15 20 25 10 15 20 25 10 15 20 25 Pseudo-first order q e (mg/g) 4.706 7.852 8.629 9.330 4.781 7.146 7.961 8.122 4.037 4.508 5.582 6.029 k 1 (1/min) 0.170 0.179 0.192 0.188 0.115 0.131 0.176 0.229 0.151 0.184 0.174 0.232 Reduced Chi-Sqr 0.006 0.017 0.075 0.0953 0.015 0.020 0.012 0.017 0.008 0.014 0.010 0.018 R-Square (COD) 0.998 0.998 0.993 0.993 0.995 0.997 0.998 0.998 0.996 0.995 0.997 0.996 Adj. R-Square 0.997 0.997 0.992 0.991 0.994 0.996 0.998 0.997 0.996 0.994 0.997 0.996 RSS 0.033 0.086 0.376 0.476 0.077 0.100 0.062 0.089 0.040 0.071 0.087 0.094 Pseudo-second order q e (mg/ g) 5.566 9.224 10.004 10.833 6.084 8.887 9.378 9.148 4.884 5.275 6.589 6.778 k 2 (g/mg/ min) 0.037 0.024 0.025 0.022 0.018 0.015 0.023 0.037 0.035 0.044 0.032 0.051 h (mg/ g/ min) 1.146 2.042 2.502 2.582 0.666 1.185 2.023 3.096 0.835 1.224 1.389 2.343 Reduced Chi-Sqr 0.002 0.007 0.006 0.030 0.007 0.001 0.006 0.009 1.03E-11 0.005 0.007 0.005 R-Square (COD) 0.999 0.999 0.999 0.997 0.997 0.999 0.999 0.999 1 0.998 0.998 0.999 Adj. R-Square 0.998 0.999 0.999 0.997 0.997 0.999 0.999 0.998 1 0.997 0.998 0.998 RSS 0.014 0.035 0.032 0.152 0.037 0.006 0.034 0.045 5.13E-11 0.027 0.038 0.026 Table 4 Estimated parametric values of Elovich and intra-particle diffusion models Model Parameters TCP (mg/L) 2,4-D (mg/L) 4-CPA (mg/L) 10 15 20 25 10 15 20 25 10 15 20 25 Elovich α (mg/ g/ min) 2.845 5.520 8.001 8.232 1.057 2.064 5.266 17.976 1.649 3.448 3.418 14.221 Β (g/mg) 0.886 0.552 0.540 0.494 0.637 0.465 0.536 0.699 0.919 0.983 0.753 0.953 Reduced Chi Sqr 0.016 0.047 0.015 0.050 0.010 0.015 0.0515 0.054 0.038 0.015 0.027 0.024 R-Square (COD) 0.995 0.995 0.998 0.996 0.996 0.997 0.994 0.994 0.984 0.995 0.994 0.995 Adj. R-Square 0.994 0.994 0.998 0.995 0.996 0.997 0.993 0.993 0.981 0.994 0.993 0.994 RSS 0.083 0.237 0.075 0.250 0.050 0.079 0.257 0.272 0.024 0.076 0.147 0.122 Intra-particle diffusion K id 0.874 1.459 1.600 1.727 0.879 1.329 1.479 1.481 0.751 0.837 1.032 1.099 C 0.515 0.919 1.107 1.180 0.215 0.457 0.909 1.303 0.357 0.544 0.615 0.975 Reduced Chi-Sqr 0.228 0.707 0.910 1.079 0.060 0.214 0.706 1.286 0.162 0.241 0.331 0.709 R-Square (COD) 0.934 0.927 0.922 0.921 0.982 0.972 0.929 0.878 0.936 0.925 0.931 0.878 Adj. R-Square 0.921 0.912 0.907 0.905 0.978 0.966 0.915 0.854 0.923 0.910 0.917 0.854 RSS 1.142 3.538 4.552 5.397 0.300 1.072 3.531 6.434 0.812 1.205 1.659 3.548 3.6. Mechanism of 2,4-D, 4-CPA and TCP degradation When the irradiation energy is higher than the band gap of TiO 2 , the photocatalytic oxidation takes place, which results in the creation of electrons and holes. The absorption of hydroxyl groups on the pTh-1’s surface, which oxidizes the organic molecules and initiates photocatalytic oxidation. As a result, the rate-limiting phase in this process has been thought to be the surface reaction (Vishnuganth et al., 2016). According to Boden-stein theory, at steady state the concentration of hydroxyl radicals and H + ions will remain unchanged. Deformation of organic complexes in the system may be traced back to the formation of OH radical, which occurred when H + and OH − ions combined to create an electron hole pair (Vishnuganth et al., 2016). $$Pesticides+{pTH}_{1}\\leftrightarrows {\\left(Pesticides-{pTH}_{1}\\right)}_{adsorb}\\to {(Herbicides-{TiO}_{2})}_{adsorb}$$ 5 $${TiO}_{2}+hv\\to \\left({TiO}_{2}\\right){e}^{-}+{h}^{+}+Heat$$ 6 $${h}^{+}+{H}_{2}O\\to {H}^{+}+{OH}^{.}$$ 7 $${e}^{-}+\\frac{1}{2}{O}_{2}+{H}^{+}\\to {OH}^{.}$$ 8 $${OH}^{.}+{\\left(Pesticides-{TiO}_{2}\\right)}_{adsorb}\\underrightarrow{hv/{TiO}_{2}}{\\left({H}_{i}-{TiO}_{2}\\right)}_{adsorb}\\to {H}_{i}+{TiO}_{2}$$ 9 In most cases, the photocatalytic process could not be started until after the adsorption-desorption equilibrium had been established. As a result, it is possible to propose the equilibrium conditions described by the following equations. $${K}_{+1}C\\left(1-{⍕}_{pesticides}-\\sum {\\text{⍕}}_{i}-{\\text{⍕}}_{{TiO}_{2}}\\right)={K}_{1}\\text{⍕}{TiO}_{2}+{K}_{-1}{\\text{⍕}}_{pesticides}$$ 10 $${K}_{+I}{C}_{i}\\left(1-{⍕}_{pesticides}-\\sum {\\text{⍕}}_{i}-{\\text{⍕}}_{{TiO}_{2}}\\right)={K}_{-i}\\text{⍕}{TiO}_{2}+{K}_{-1}{\\text{⍕}}_{pesticides}$$ 11 where pesticides refer to TCP, 4-CPA and 2,4-D respectively; hv is the photon energy from UV light; h + and e − refers to the holes and electrons; ⍕ pesticides and ⍕TiO 2 are the fractional coverage of the pesticides and TiO 2 on pTH-1’s surface respectively. C and C i are the concentration of pesticides and intermediates (mg/L) whereas K + 1 and K − 1 rate constants of adsorption and desorption, respectively. When the aforementioned process is taken into consideration, it is pertinent to assert that the photocatalytic degradation owing to the oxidizing of intermediate products by the OH radicals present on the pTh-1’s surface (Zhang et al., 2011). 3.7. Energy consumption and economic analysis Photocatalysis of pesticides is one that requires a significant amount of electrical energy and accounts for a significant portion of the overall operating costs (Cater et al., 2000; Vishnuganth et al., 2016). E EO may be determined for a batch type reactor by utilizing the equation that is shown below (Daneshvar et al., 2005); $${E}_{E0}=\\frac{P\\times t\\times 1000}{V\\times 60\\times log\\left(\\frac{{C}_{0}}{{C}_{f}}\\right)}$$ 12 The preceding equation has an implied connection to the L-H model's first order kinetics as follows: $$ln\\left(\\frac{{C}_{0}}{{C}_{t}}\\right)={k}_{obs}t$$ 13 By combining the above equations, E EO can be expressed as; $${E}_{E0}=\\frac{P\\times 38.4}{V\\times {k}_{obs}t}$$ 14 Eq. ( 14 ) are used for determining the amount of electrical energy required to complete one order in an idealized batch reactor. The experimental results for determining E EO for the elimination of pesticides using the pTh-1 photocatalysis system are presented in Table 5 . Value of E EO increased with raise in the pesticide’s concentrations (Cater et al., 2000; Vishnuganth et al., 2016). The fact that the value of E EO from the kinetic model matches with the value from the experimental data describing that the process followed first-order kinetics. Table 5 Cost estimates for the removal of TCP, 2,4-D and 4-CPA by pTh-1 Pesticides Concentration (mg/L) pH Catalyst load (g/L) Cost ₹/kg removal TCP 10 4.3 1.0 60,678 15 4.3 1.0 50,695 20 4.3 1.0 40,644 25 4.3 1.0 34,923 10 7.0 1.0 1,00,312 10 8.8 1.0 2,04,986 10 4.3 0.5 1,00,312 10 4.3 1.5 69,333 2,4-D 10 4.9 1.0 54,822 15 4.9 1.0 39,786 20 4.9 1.0 30,615 25 4.9 1.0 25,834 10 8.2 1.0 76,043 10 10.8 1.0 5,23,852 10 4.9 0.5 76,043 10 4.9 1.5 56,127 4-CPA 10 4.8 1.0 51,810 15 4.8 1.0 37,869 20 4.8 1.0 29,727 25 4.8 1.0 25,145 10 6.0 1.0 57,182 10 9.3 1.0 61,071 10 4.8 0.5 60,803 10 4.8 1.5 55,078 The sum of capital, operational and maintenance expenses are used to calculate the total costs, which is dependent on the type of pollutant, its concentration and the reactor, designs. Because of this, the evaluation of the costs was predicated on the figure-of-merit (E EO ) that was computed for each individual batch of experimental runs (Esplugas et al., 2002; Remya and Lin 2011). Operating cost (total) under optimum circumstances such as pTh-1 load, pesticide concentration, pH, reaction time with constant UV intensity were calculated using the following relations; $$Operating cost \\left(₹/kg\\right)=\\frac{Energy consumed \\left(kWh\\right)\\times unit cost (₹/kWh)\\times {10}^{6}}{pesticide removal \\left(mg\\right)}$$ 15 $$Energy consumed \\left(kWh\\right)=\\frac{Power input \\left(kW\\right)\\times Reaction time \\left(min\\right)}{1000\\times 60}$$ 16 Table 5 is a tabulation of the total operating cost that is required for the removal of one kilogram of pesticides from contaminated water and inputs considered for cost calculation is provided in the Supplementary Materials Experimental S3. It was noticed that the total operating cost, expressed in terms of rupees per kilogram, decreases in proportion to increases in the initial pesticide concentration (Asha et al., 2015). 3.8. Reusability of pTh-1 Reuse of an adsorbent or catalyst is what affects the practical viability and the cost of a treatment approach from a technological and economic perspective. Within the scope of this investigation, pTh-1’s reusability was investigated by carrying out five consecutive photodegradation cycles in ideal conditions. Recovered composite was washed, dried at 70°C prior being employed in the next cycle. After five consecutive cycles, the photo-degradation efficiency of pTh-1 declined from, 86 to 79%, 91.6 to 83% and 78 to 70% during the removal of 2,4-D, 4-CPA and TCP as shown in the Supplementary Materials Figure S4. Results of the reusability tests indicate that the pTh-1 material has a substantial repeatability, although there is a slight decrease in photo-degradation after three-cycles of operations. This could be attributed to particle aggregation during catalysis or catalyst loss while recovering, but the decrease is still relatively small (Li et al., 2008; Rathod et al., 2018). 4. Conclusions In this study, we have described the production of a functionalized pTh-TiO 2 nanocomposites using oxidative polymerization using different proportions of TiO 2 . pTh-1 nanocomposite exerted better removal efficiencies when compared with other materials and was able to adsorb with concomitant photocatalytic breakdown of three distinct pesticides within 120 min. The different sorption equilibria, kinetics were evaluated for the removal of 2,4-D, 4-CPA and TCP using empirical models. While L-H model described the removal of pesticides using pTH-1 through photo-degradation. Conclusively, the reusability of the nano-composites and process economics for the pesticide removal were evaluated. Declarations Ethical approval and consent to participate: The authors declare that they have no known competing financial interests or personal relationships that seem to affect the work reported in this article. Consent for Publication: We do not have any individual person’s data in any form. Availability of data and materials: Not applicable Competing interest: The authors declare that they have no conflict of interest. Funding: Not applicable Authors’ contribution Pareshkumar G Moradeeya: Investigation and writing-original draft. Madhava Anil Kumar: Conceptualization, writing-original draft. Archana Sharma: review and editing. Shaik Basha: Supervision, Writing-Review & Editing. All authors read and approved the manuscript. Acknowledgement The authors would like to extend their gratitude to the Director of CSIR-NEERI and Director of CSIR-CSMCRI, as well as the Management of Marwadi University, for the help they have provided. The manuscript has been given the reference number CSIR-NEERI/KRC/2022/JUNE/HZC/1. References Alalm MG, Tawfik A, Ookawara S (2015) Comparison of solar TiO 2 photocatalysis and solar photo-Fenton for treatment of pesticides industry wastewater: operational conditions, kinetics, and costs. J Water Process Eng 8: 55–63. https://doi.org/10.1016/j.jwpe.2015.09.007 Ansari MO, Khan MM, Ansari SA, Cho MH (2015) Polythiophene nanocomposites for photodegradation applications: Past, present and future. J Saudi Chem Soc 19: 494–504. https://doi.org/10.1016/j.jscs.2015.06.004 Arabahmadi V, Ghorbani M (2017) Surface modified polythiophene nanocomposite using HPC and DBSNa for heavy metal ion removal. 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Catal Sci Technol 11, 6630–6648. https://doi.org/10.1039/D1CY01129D Supplementary Files Graphicalabstract.docx SupplementaryMaterials.docx 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. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {\"props\":{\"pageProps\":{\"initialData\":{\"identity\":\"rs-1839933\",\"acceptedTermsAndConditions\":true,\"allowDirectSubmit\":true,\"archivedVersions\":[],\"articleType\":\"Research Article\",\"associatedPublications\":[],\"authors\":[{\"id\":127109328,\"identity\":\"046b3548-6d77-42ea-8c41-5fee2466f072\",\"order_by\":0,\"name\":\"Pareshkumar Moradeeya\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"CSIR-NEERI: National Environmental Engineering Research Institute CSIR\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Pareshkumar\",\"middleName\":\"\",\"lastName\":\"Moradeeya\",\"suffix\":\"\"},{\"id\":127109329,\"identity\":\"03375c7f-4d3b-412d-98e6-ce3754adf551\",\"order_by\":1,\"name\":\"Anil Kumar Madhava\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"CSIR-CSMCRI: Central Salt and Marine Chemicals Research Institute CSIR\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Anil\",\"middleName\":\"Kumar\",\"lastName\":\"Madhava\",\"suffix\":\"\"},{\"id\":127109330,\"identity\":\"486dcca6-9150-48fb-ab7b-e5d0e9be1196\",\"order_by\":2,\"name\":\"Archana Sharma\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Marwadi University\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Archana\",\"middleName\":\"\",\"lastName\":\"Sharma\",\"suffix\":\"\"},{\"id\":127109331,\"identity\":\"7d5fbe7b-a9ce-4e3e-9e9d-77b90a821fbc\",\"order_by\":3,\"name\":\"Shaik Basha\",\"email\":\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA20lEQVRIiWNgGAWjYFACHgYGxgYGOTA7AUwCucRoMSZdSyIhZQgg38B78OPPHXbp29mbj314wHBPTr6Bue0BPi0GB/iSpXnPJOfu7DmWPCOBodjY4ABjuwFeLQw8BtKMbcy5G27kGAP9kpC4gYGxTQK/w3iMf/5sq083uP/+M0hL/fwGAloYDvCYSfC2HU4wuMHDDNKSwHCAgBagX9KseduOG244kwZ0mEGC4YbDBB3Ge/jmz7ZqeYPjhx8z/qhIkJdvb3+G32HyD1AsBWJmvOpHwSgYBaNgFBADACdsRGYuBQV7AAAAAElFTkSuQmCC\",\"orcid\":\"\",\"institution\":\"National Environmental Engineering Research Institute CSIR\",\"correspondingAuthor\":true,\"prefix\":\"\",\"firstName\":\"Shaik\",\"middleName\":\"\",\"lastName\":\"Basha\",\"suffix\":\"\"}],\"badges\":[],\"createdAt\":\"2022-07-08 17:52:19\",\"currentVersionCode\":1,\"declarations\":\"\",\"doi\":\"10.21203/rs.3.rs-1839933/v1\",\"doiUrl\":\"https://doi.org/10.21203/rs.3.rs-1839933/v1\",\"draftVersion\":[],\"editorialEvents\":[],\"editorialNote\":\"\",\"failedWorkflow\":false,\"files\":[{\"id\":25002277,\"identity\":\"cf6febf6-40bf-4377-bb61-a3f98d0a40c1\",\"added_by\":\"auto\",\"created_at\":\"2022-08-09 18:18:19\",\"extension\":\"png\",\"order_by\":1,\"title\":\"Figure 1\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":114003,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e(a) UV-vis spectra and (b) Tauq plot of pure TiO\\u003csub\\u003e2\\u003c/sub\\u003e and pTh-1\\u0026nbsp;\\u003c/p\\u003e\\u003cp\\u003e\\u003cbr\\u003e\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"1.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-1839933/v1/cfc63d0becbae287ce57829b.png\"},{\"id\":25001539,\"identity\":\"799ce12a-f416-4c87-924d-a6175478ec5b\",\"added_by\":\"auto\",\"created_at\":\"2022-08-09 18:03:19\",\"extension\":\"png\",\"order_by\":2,\"title\":\"Figure 2\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":84911,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003eSelection of photocatalyst (a) 2,4-D, (b) 4-CPA and (c) TCP (\\u003cem\\u003eC\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003eo\\u003c/em\\u003e\\u003c/sub\\u003e: 10 mg/L; T: 298 K; \\u003cem\\u003et\\u003c/em\\u003e: 120 min; I: 10 W/m\\u003csup\\u003e2\\u003c/sup\\u003e; TiO\\u003csub\\u003e2 \\u003c/sub\\u003e, pTh-1, pTh-2, pTh-3: 1.0 g/L)\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"2.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-1839933/v1/61e7950c30b6d23bfc6adcb8.png\"},{\"id\":25002111,\"identity\":\"a780f330-b0f6-4a1e-b559-2b95756f3ff6\",\"added_by\":\"auto\",\"created_at\":\"2022-08-09 18:13:20\",\"extension\":\"png\",\"order_by\":3,\"title\":\"Figure 3\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":114649,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003epH effect on adsorption-photocatalysis (a) 2,4-D, (b) 4-CPA and (c) TCP (\\u003cem\\u003et\\u003c/em\\u003e: 30 min; T: 298 K; pTh-1: 1.0 g/L)\\u003c/p\\u003e\\u003cp\\u003e\\u003cbr\\u003e\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"3.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-1839933/v1/23a596c6b5eb0e2f79ab0820.png\"},{\"id\":25001998,\"identity\":\"03dc369f-4181-44ec-a1e2-570d21b5cb87\",\"added_by\":\"auto\",\"created_at\":\"2022-08-09 18:08:20\",\"extension\":\"png\",\"order_by\":4,\"title\":\"Figure 4\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":139232,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003eEffect of pTh-1 dose on photodegradation (a) 2,4-D, (b) 4-CPA and (c) TCP (\\u003cem\\u003et\\u003c/em\\u003e: 30 min; T: 298 K; pTh-1: 0.5-1.5 g/L)\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"4.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-1839933/v1/3226d1514dd90c359a3f7913.png\"},{\"id\":25001995,\"identity\":\"890d59e7-3ff6-49a6-b735-7c5d8eeca18c\",\"added_by\":\"auto\",\"created_at\":\"2022-08-09 18:08:19\",\"extension\":\"png\",\"order_by\":5,\"title\":\"Figure 5\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":131653,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003eEffect of initial concentration on photodegradation (a) 2,4-D, (b) 4-CPA and (c) TCP (\\u003cem\\u003et\\u003c/em\\u003e: 30 min; T: 298 K; pTh-1: 1.0 g/L)\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"5.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-1839933/v1/3bda0b04cc92a9962a99fbcf.png\"},{\"id\":25001546,\"identity\":\"4bc38241-7c9e-4f17-8f5e-3bffefc2c830\",\"added_by\":\"auto\",\"created_at\":\"2022-08-09 18:03:20\",\"extension\":\"png\",\"order_by\":6,\"title\":\"Figure 6\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":137499,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003eIsotherm trend of (a) 2,4-D, (b) 4-CPA and (c) TCP (\\u003cem\\u003et\\u003c/em\\u003e: 30 min; T: 298 K; pTh-1: 1.0 g/L)\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"6.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-1839933/v1/32bf9ace3dc91c59d52c134c.png\"},{\"id\":25002109,\"identity\":\"ac22d0be-0cc3-403b-807b-f2ae5a382551\",\"added_by\":\"auto\",\"created_at\":\"2022-08-09 18:13:19\",\"extension\":\"png\",\"order_by\":7,\"title\":\"Figure 7\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":166633,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003ePseudo-second order kinetic profile for (a) 2,4-D, (b) 4-CPA and (c) TCP (\\u003cem\\u003et\\u003c/em\\u003e: 30 min; T: 298 K; pTh-1: 1.0 g/L)\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"7.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-1839933/v1/5e0e3b166db817058442256f.png\"},{\"id\":28063257,\"identity\":\"d6559efe-eca8-410b-b032-aba3b1502de2\",\"added_by\":\"auto\",\"created_at\":\"2022-10-20 21:25:26\",\"extension\":\"pdf\",\"order_by\":0,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"manuscript-pdf\",\"size\":1384012,\"visible\":true,\"origin\":\"\",\"legend\":\"\",\"description\":\"\",\"filename\":\"manuscript.pdf\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-1839933/v1/c5cc2f1e-62a8-4a6f-90a1-fd3b4b6c9ec8.pdf\"},{\"id\":25001543,\"identity\":\"42fc38e8-4bd0-4038-b38f-be9cbea087e1\",\"added_by\":\"auto\",\"created_at\":\"2022-08-09 18:03:19\",\"extension\":\"docx\",\"order_by\":1,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":137992,\"visible\":true,\"origin\":\"\",\"legend\":\"\",\"description\":\"\",\"filename\":\"Graphicalabstract.docx\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-1839933/v1/4d7f7de68a9e9f00fd4bc78a.docx\"},{\"id\":25002112,\"identity\":\"e5e4bdb7-8109-4f35-a5de-8306743a01cc\",\"added_by\":\"auto\",\"created_at\":\"2022-08-09 18:13:20\",\"extension\":\"docx\",\"order_by\":2,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":2045247,\"visible\":true,\"origin\":\"\",\"legend\":\"\",\"description\":\"\",\"filename\":\"SupplementaryMaterials.docx\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-1839933/v1/8a2290046aac213c42543238.docx\"}],\"financialInterests\":\"\",\"formattedTitle\":\"Sorption-photocatalysis of structurally distinct pesticides using polythiophene/TiO2 composites: Kinetics, equilibrium, reusability and operational economics\",\"fulltext\":[{\"header\":\"1. Introduction\",\"content\":\"\\u003cp\\u003eThe availability of pure and wholesome water is both a significant concern for human life. However, sewage and industrial effluent that is dumped into the environment degrade fresh drinking water, making it impossible to provide clean water to residents and ecosystems in the surrounding area (Mohamed et al., 2018). Various types and amounts of water contaminants, organic compound (dyes, pesticides, pharmaceutical residual, and petrochemicals-hydrocarbon), inorganic compounds (heavy metals, ammonia, phosphates and chemical fertilizers) commonly found in discharged wastewater (Moradeeya et al., 2022a; Mohamed et al., 2018). Water contamination by synthetic pesticides is one of the most serious issues confronting environmental protection measures (Lam et al., 2018). Herbicides are poisonous organic compounds with a limited biodegradability that are responsible for a variety of environmental issues such as aesthetic loss, high pollution load, eutrophication, and aquatic system disturbances (Nitschke et al., 1999; Shelton and Miller, 2002). Pesticides contaminate the aquatic environment in a variety of ways, including runoff, leaching, and spray drift, all of which pose substantial health concerns to both the terrestrial and aquatic ecosystems. All layers of biological organization, including primary producers, microbes, invertebrates and fishes, are immediately affected by this exposure. Furthermore, chlorinated organic compounds, as contaminants in available water sources, can cause the water's health to deteriorate and has been linked to increased risk of cancer and mutations in humans as well as wildlife (Carpenter, 2011; Ashraf, 2017).\\u003c/p\\u003e \\u003cp\\u003eIn order to mitigate the damage that herbicides and other contaminants might do, a few different approaches have been tried to remove them from water supplies. There are a variety of methods that can be applied, including adsorption, coagulation, flocculation, advanced oxidation, and bioremediation (Moradeeya et al., 2022a). Herbicide adsorption removal is easy and involve low-maintenance and the amount of sludge produced is less than with other procedures (Moradeeya et al., 2017). It was also suggested that advanced oxidation of herbicides would be an effective strategy, however the combined adsorption photocatalysis method is more promising in terms of cost and toxicity reduction (Sheng et al., 2019; Chang et al., 2020; Fazal, et al., 2020;). Straightforward photolysis of oxidants such as hydrogen peroxide or ozone under the influence of UV illumination, homogeneous (Fenton and photo-Fenton) and heterogeneous photocatalytic degradation are the technique for removing pesticides (Moradeeya et al., 2022b; Alalm et al., 2015; Zanoni et al., 2022). Titanium dioxide (TiO\\u003csub\\u003e2\\u003c/sub\\u003e) is a commonly used photocatalyst and the most significant disadvantage is the difficulty to remove them from solution. TiO\\u003csub\\u003e2\\u003c/sub\\u003e particle adhesion to particular surfaces has been suggested as a solution to the problem of photocatalyst removal from reaction media (Ong et al., 2014; Perović, et al., 2020; Wang et al., 2020). Nanostructured polymers with adsorption and photocatalytic characteristics have attracted a lot of attention in the field of water treatment (Riaz et al., 2015; El-Bery et al., 2021).\\u003c/p\\u003e \\u003cp\\u003eWith the aforementioned problem, the presented research aims to fabricate polythiohene (pTh) coated TiO\\u003csub\\u003e2\\u003c/sub\\u003e nanocomposites and to evaluate their efficacies in removing three structurally distinct chlorinated phenoxyacetic acid (herbicides) from aqueous solutions. Thus, our work seeks to construct nanopolymer polythiophene on the surface of the titanium dioxide using an \\u003cem\\u003ein-situ\\u003c/em\\u003e polymerization technique to create (pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e) for the adsorption and photocatalytic removal of acidic herbicides from water. To perform photolysis using the fabricated nanocomposites under ultraviolet (UV) light as a function of catalyst stability, herbicide\\u0026rsquo;s concentrations, illumination time, solution pH, catalyst dose, and role of the combination process. To elucidate the pesticides removal mechanism using kinetic and equilibrium models.\\u003c/p\\u003e\"},{\"header\":\"2. Experimental\",\"content\":\"\\u003cdiv id=\\\"Sec3\\\" class=\\\"Section2\\\"\\u003e\\u003ch2\\u003e2.1. Materials\\u003c/h2\\u003e \\u003cp\\u003e4-chlorophenoxyacetic acid (4-CPA) and 2,4-Dichlorophenoxyacetic acid (2,4-D) were purchased from Otto Chemical, (India) while Triclopyr Acid (TCP) was kindly given by Aimco Pesticides (India). Thiophene was procured from Sigma Aldrich while HCl, chloroform and NaOH were products of Qualigens (India). Water HPLC grade and methanol were used for the chromatographic analytical tests and non-sterile Millex\\u0026reg; syringe filters (0.45 \\u0026micro;m) were used in this study. A methanol/water mix system was used to make the pesticide standard stocks, which were then diluted in distilled water to make the final concentrations.\\u003c/p\\u003e \\u003c/div\\u003e \\u003cdiv id=\\\"Sec4\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e2.2. Preparation and characterization of coated nanocomposites\\u003c/h2\\u003e \\u003cp\\u003epTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e nano-composites were fabricated using the method described by Cao et al. (2020) with slightly modification. Varying amount of TiO\\u003csub\\u003e2\\u003c/sub\\u003e (1.6, 3.2 and 4.8 g) and 20 mL of chloroform was mixed in an ultrasonic bath for 15 min. To this mixture, 0.21 mL of thiophene was added and stirred for 30 min; further FeCl\\u003csub\\u003e3\\u003c/sub\\u003e solution (5 g in 60 mL chloroform) was added drop wise in the TiO\\u003csub\\u003e2\\u003c/sub\\u003e/thiophene solution, which was placed for a further 24 h under stirring under cooling in an ice bath. After 24 h, the reaction mixture was filtered to collect the black-reddish precipitate, which was washed with distilled water once, followed by alternate wash with methanol, 1.0 N HCl. The washing was repeated until filtrate become colorless, and nonreactive, then placed in an oven at 70\\u0026deg;C for 24 h for drying. Resultant materials were designated as pTh-1, pTh-2 and pTh-3. The fabricated materials were characterized using different analytical instrumentation as described in the Supplementary Materials Experimental S1\\u0026amp;S2.\\u003c/p\\u003e \\u003c/div\\u003e \\u003cdiv id=\\\"Sec5\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e2.3. Batch sorption tests\\u003c/h2\\u003e \\u003cp\\u003eThe photocatalytic activity of pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e was examined for herbicide degradation using UV light irradiation from a high-pressure mercury lamp (365 nm light). Adsorption and photocatalysis experiments were conducted at room temperature in a borosilicate glass photochemical reactor with an immersion well. For a period of thirty minutes, adsorption studies were carried out in utter darkness before photodegradation tests were performed in order to ascertain the extent to which adsorption contributed to the overall removal rate of pesticides. Subsequently attaining adsorption equilibrium, pesticides with pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e mixtures were exposed to UV light for photocatalytic destruction. The screening assays used 1.0 g/L of pTh (pTh-1, pTh-2 and pTh-3) with fixed pesticide concentration of 10 mg/L. Aliquots were withdrawn at various time interval, filtered and estimated the removal percentage.\\u003c/p\\u003e \\u003c/div\\u003e \\u003cdiv id=\\\"Sec6\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e2.4. Effect of process parameters on removal efficiencies\\u003c/h2\\u003e \\u003cp\\u003eThe effect of process parameters such as catalyst dose, pH value, irradiation time and initial herbicides concentrations on sorption-photocatalysis were evaluated using \\u003cem\\u003eone-factor-at-a-time\\u003c/em\\u003e approach. The varying concentrations of the catalyst (0.5\\u0026ndash;1.5 g/L), pH (4.3\\u0026ndash;10.8) and individual herbicides concentrations (10\\u0026ndash;25 mg/L) in 50 mL of the reaction volume. The batch reactions were agitated at 150 rpm and residual concentrations were estimated at different time (30 min for adsorption and 120 min for photodegradation).\\u003c/p\\u003e \\u003c/div\\u003e \\u003cdiv id=\\\"Sec7\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e2.5. Equilibrium studies\\u003c/h2\\u003e \\u003cp\\u003eThe adsorption equilibrium of by the pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e nanocomposites were investigated to understand the adsorption mechanism and the proficiency of the fabricated nanocomposites. For this purpose, 1.0 g/L pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e nanocomposites was agitated with 50 mL of 2,4-D, 4-CPA and TCP solutions (10\\u0026ndash;25 mg/L) individually for 30 min. The residual concentrations of the pesticides were quantitatively assessed using high performance liquid chromatography (HPLC) and the observed equilibrium uptake were fitted to the different isotherm models \\u003cem\\u003eviz.\\u003c/em\\u003e, Langmuir, Freundlich, Redlich-Peterson and Sips.\\u003c/p\\u003e \\u003c/div\\u003e \\u003cdiv id=\\\"Sec8\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e2.6. Kinetics studies\\u003c/h2\\u003e \\u003cp\\u003eThe effect of contact duration on herbicides (2,4-D, 4-CPA and TCP) adsorption by pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e was examined by shaking 1.0 g/L of pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e with 50 mL of 10\\u0026ndash;25 mg/L individual herbicide solution under restricted light source for 30 min. Aliquots were withdrawn to assess the residual concentrations of 2,4-D, 4-CPA and TCP. The observed data were fitted to different kinetic and isotherm models to describe the adsorption behavior of pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e nanocomposites. Langmuir-Hinshelwood rate determines the interrelationship between the initial degradation and concentration of the pollutants (Krishnakumar and Swaminathan, 2011).\\u003cdiv id=\\\"Equ1\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ1\\\" name=\\\"EquationSource\\\"\\u003e\\n$$\\\\frac{1}{{k}_{app}}=\\\\frac{1}{{k}_{c }{K}_{LH}}+\\\\frac{{C}_{0}}{{k}_{c}}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e1\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e \\u003cp\\u003ewhere \\u003cem\\u003eC\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003e0\\u003c/em\\u003e\\u003c/sub\\u003e is the initial concentration (mg/L) of the pollutant, \\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003eLH\\u003c/em\\u003e\\u003c/sub\\u003e is the Langmuir-Hinshelwood adsorption equilibrium constant (mg/L) whereas \\u003cem\\u003ek\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003ec\\u003c/em\\u003e\\u003c/sub\\u003e is rate constant (mg/L/min).\\u003c/p\\u003e \\u003c/div\\u003e \\u003cdiv id=\\\"Sec9\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e2.7. Evaluation of catalyst\\u0026rsquo;s stability\\u003c/h2\\u003e \\u003cp\\u003eOne of the most important requirements for commercial use of a synthetic catalyst is its stability and reusability for several cycles of herbicide removal. Stirring 1.0 g/L of pTh-1 with 50 mL of individual herbicide solutions (10 mg/L) for five cycles was used to examine this. The composite powder was rinsed with distilled water, methanol and diluted HCl after each cycle and dried at 70\\u0026deg;C for 180 min before being utilized in the following cycle.\\u003c/p\\u003e \\u003c/div\\u003e\"},{\"header\":\"3. Results And Discussion\",\"content\":\"\\u003cdiv id=\\\"Sec11\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e3.1. Synthesis and characterization of pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e nanocomposites\\u003c/h2\\u003e \\u003cp\\u003eDiffraction patterns of TiO\\u003csub\\u003e2\\u003c/sub\\u003e and pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e (Supplementary Materials Figure S1) shows the crystalline nature of anatase TiO\\u003csub\\u003e2\\u003c/sub\\u003e (Mahlake et al., 2019). The major peaks are located at crystal planes (101), (004), (200), (105), (211) and (204) which is consistent with the applicable standard reference (Li et al., 2014). XRD pattern of pTh-1 shows almost identical strong diffraction peaks at the corresponding position of pure TiO\\u003csub\\u003e2\\u003c/sub\\u003e in polythiophene matrix. Simultaneously, no new diffraction peaks appeared in the pattern of the synthesized composites, probably due to the low polythiophene content of the composites (Xu et al., 2010; Chen et al., 2018). However, the presence of polythiophene, the diffraction peak strength fell marginally implying the negligible effect of polythiophene on TiO\\u003csub\\u003e2\\u003c/sub\\u003e coating.\\u003c/p\\u003e\\u003cp\\u003eThe morphology of TiO\\u003csub\\u003e2\\u003c/sub\\u003e and pTh-1 was studied using FE-SEM, with images acquired at 5 KX and 100KX magnifications, as shown in the Supplementary Materials Figure S2. Images show that the TiO\\u003csub\\u003e2\\u003c/sub\\u003e are homogeneous and seem to be agglomerated. The composite\\u0026rsquo;s surface activity increased due to the high surface-to-volume ratio, resulting in a greater degree of UV light absorption. Polythiophene distribution across TiO\\u003csub\\u003e2\\u003c/sub\\u003e is consistent, implying that the pTh-1 composite is made up of granular complexes. Because of the loose and porous character of pTh-1 resulting in overall roughness, its adsorption and/or photocatalysis efficacy is greatly boosted.\\u003c/p\\u003e \\u003cp\\u003eTo demonstrate the typical peaks of the products, IR spectra of pure TiO\\u003csub\\u003e2\\u003c/sub\\u003e and pTh-1 samples were examined, and the findings are shown in Supplementary Materials Figure S3. FT-IR spectra of TiO\\u003csub\\u003e2\\u003c/sub\\u003e had three major absorption peaks can be recognized between 3435 and 1630 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e due to OH groups (Zhang et al., 2019; Praveen et al., 2014). Some of the distinctive peaks given to pTh are faint in the composite, possibly due to overlap with strong peaks ascribed to TiO\\u003csub\\u003e2\\u003c/sub\\u003e. Furthermore, due to the impact of OH, the loading rate of pTh may be decreased when the reaction is carried out in aqueous medium (Chen et al., 2018; Roncali, 1992). Peaks at 695 and 784 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e are often attributed to the C\\u0026ndash;H out-of-plane deformation (Shoubin et al., 2011). C-S bond, which is the presence of thiophene monomer in the polymer backbone, corresponds to the absorption of 697 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e (Martinez et al., 2000). A stretching vibration of C-C bonds is most likely responsible for the band about 1350 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e. In polythiophene, the stretching frequency of the C\\u0026thinsp;=\\u0026thinsp;C bond is between 1443 and 1523 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e. Several faint peaks in the 2800\\u0026ndash;3100 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e and 1690 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e ranges can be ascribed to C\\u0026ndash;H and C\\u0026thinsp;=\\u0026thinsp;C characteristic peaks, respectively (Shoubin et al., 2011). It's worth noting that the peaks at 1676 cm\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e in the spectra of pTh might potentially be attributed to C\\u0026thinsp;=\\u0026thinsp;O (Chen et al., 2018).\\u003c/p\\u003e \\u003cp\\u003eUV-vis spectra of pure TiO\\u003csub\\u003e2\\u003c/sub\\u003e and pTh-1 Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ea showed strong ultraviolet (UV) absorption with a peak and the visible range (In pTh-1). Photo-generation by TiO\\u003csub\\u003e2\\u003c/sub\\u003e is linked to a significant signal focused in the UV zone in the spectrum of pTh-1 nanocomposite, where a notable peak is detected around the visible zone, which is related with the π\\u0026rarr;π* electronic transitions of delocalized pi-bonds (Ansari et al., 2015). The absorption peak at 700 nm has vanished, but there is a noticeable rise in absorption between UV and visible region (Xu et al., 2010). Because of the polythiophene coating on the surface of TiO\\u003csub\\u003e2\\u003c/sub\\u003e, the UV area moves toward the region of visible wavelength. pTh-1\\u0026rsquo;s absorption peak has a red shift, indicating that it is a promising candidate for organic pollutant degradation when exposed to UV, visible, and solar radiation. According to Tauc\\u0026rsquo;s plot (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003eb), the band-gap energies for pure TiO\\u003csub\\u003e2\\u003c/sub\\u003e and pTh-1 were 3.2 and 1.9 eV, respectively. The photo-induced charge transfer from polythiophene to TiO\\u003csub\\u003e2\\u003c/sub\\u003e can be accelerated by this interaction (Zia et al., 2021). As a result of the polythiophene coating on TiO\\u003csub\\u003e2\\u003c/sub\\u003e, the photocatalytic effectiveness was improved.\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e \\u003c/div\\u003e \\u003cdiv id=\\\"Sec12\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e3.2. Screening of composites\\u003c/h2\\u003e \\u003cp\\u003eThe screening of nanocomposites was carried out to evaluate the most optimal weight ratio of TiO\\u003csub\\u003e2\\u003c/sub\\u003e in the synthesis during the fabrication of pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e. The photocatalytic degradation efficiencies of pTh-1, pTh-2, PTh-3 and unaltered TiO\\u003csub\\u003e2\\u003c/sub\\u003e under UV light are illustrated in the Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003e. The adsorption efficiency of pTh composites were arranged in the order of better efficacies: pTh-1\\u0026thinsp;\\u0026gt;\\u0026thinsp;pTh-2\\u0026thinsp;\\u0026gt;\\u0026thinsp;pTh-3\\u0026thinsp;\\u0026gt;\\u0026thinsp;TiO\\u003csub\\u003e2\\u003c/sub\\u003e. As a result, pTh-1 was chosen for future inquiry, and the activities of the nanocomposites were clearly higher than bare TiO\\u003csub\\u003e2\\u003c/sub\\u003e after adsorption-desorption equilibrium and irradiation. Reaction sets showed strong adsorption within 30 min, which is consistent with the findings, which explained why the nanocomposite outperformed the naked TiO\\u003csub\\u003e2\\u003c/sub\\u003e. The surface modification of TiO\\u003csub\\u003e2\\u003c/sub\\u003e with polythiophene improves the photo-response of the pTh-1 nanocomposites.\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e \\u003c/div\\u003e \\u003cdiv id=\\\"Sec13\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e3.3. Effect of process variables on sorption-photocatalysis\\u003c/h2\\u003e \\u003cp\\u003eAqueous reaction mixtures containing the individual pesticides as well as the pTh-1 are influenced by solution\\u0026rsquo;s pH. Effect of initial pH on the sorption capacity of composite was explored in pH 4.3\\u0026ndash;10.8 for better elucidation. Acidic pH levels are more favorable for selected three herbicides in adsorption (data not shown), similar trend observed by others (Palma et al., 2015; Nematollahzadeh et al., 2021). Protonation-deprotonation of composite functional groups are affected by pH fluctuations. Sorption was significantly facilitated by the acidic environment, and surface functionalization was encouraged by the decreased pH of the solution throughout the contacting process. On the polymer chain, an electrostatic potential distribution is formed, and the sites with defect states become adsorption active (Moradeeya et al., 2022b; Nematollahzadeh et al., 2021). It was observed that the sorption-photocatalytic activity of the pTh-1 was reduced when the solution\\u0026rsquo;s pH increased, and the catalyst showed the highest level of efficacy at an acidic pH as shown in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003e. An important factor in the formation of the pTh-1's net surface charge is its protonation and deprotonation at acidic and basic pH levels.\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e \\u003cp\\u003eThe effect of the dose of pTh-1 (0.5\\u0026ndash;1.5 g/L) on the photodegradation of 2,4-D, 4-CPA and TCP was tested using a constant concentration of the aforementioned pesticides (10 mg/L) at the ideal pH over a length of time of 120 min. The findings are presented in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003e, which illustrates a comparison of the entire reaction involving adsorption and photocatalysis increases, whereas photo-degradation efficiency declines, with rise in the catalyst dosage. Aggregation of the photocatalyst, which leads to a smaller available surface area on the photocatalyst for photon absorption, may have contributed to a decrease in the effectiveness of the degradation process when a high dose was used (Malato et al., 2009). Initially, the rate of adsorption is faster due to available number of active site and splitting effect of the flux between pTh-1 and the tested pesticides.\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e \\u003cp\\u003eInitial pesticide concentration influences the kinetic rate constant, which decreases with increasing initial pesticide concentration (Moradeeya et al., 2022b). The tests on the decomposition of pesticides by UV irradiation follow the pseudo-first order kinetics with regard to the concentration of pesticides in the solution phase.\\u003cdiv id=\\\"Equ2\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ2\\\" name=\\\"EquationSource\\\"\\u003e\\n$$\\\\text{r}=-\\\\frac{d\\\\text{C}}{dt}=\\\\frac{{\\\\text{K}}_{\\\\text{a}\\\\text{d}\\\\text{s}}{k}_{\\\\text{L}-\\\\text{H}}\\\\text{C}}{1+{\\\\text{K}}_{\\\\text{a}\\\\text{d}\\\\text{s}}\\\\text{C}}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e2\\u003c/div\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Equ3\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ3\\\" name=\\\"EquationSource\\\"\\u003e\\n$$\\\\text{r}=-\\\\frac{d\\\\text{C}}{dt}={\\\\text{K}}_{\\\\text{a}\\\\text{d}\\\\text{s}}{k}_{\\\\text{L}-\\\\text{H}}\\\\text{C}={k}_{app}\\\\text{C}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e3\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e \\u003cp\\u003eApplying the limits of \\u003cem\\u003eC\\u0026thinsp;=\\u0026thinsp;C\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003e0\\u003c/em\\u003e\\u003c/sub\\u003e at \\u003cem\\u003et\\u0026thinsp;=\\u0026thinsp;0\\u003c/em\\u003e with \\u003cem\\u003eC\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003e0\\u003c/em\\u003e\\u003c/sub\\u003e being the starting concentration in the solution phase and \\u003cem\\u003et\\u003c/em\\u003e being the reaction time;\\u003cdiv id=\\\"Equ4\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ4\\\" name=\\\"EquationSource\\\"\\u003e\\n$$ln\\\\left(\\\\frac{{C}_{0}}{{C}_{t}}\\\\right)={k}_{app}t$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e4\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e \\u003cp\\u003ewhere, \\u003cem\\u003ek\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003eapp\\u003c/em\\u003e\\u003c/sub\\u003e is the apparent rate constant influenced by the pesticide\\u0026rsquo;s concentration. Figure\\u0026nbsp;\\u003cspan refid=\\\"Fig5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003e depicts a plot of the natural logarithm of the concentration ratio \\u003cem\\u003eC\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003e0\\u003c/em\\u003e\\u003c/sub\\u003e\\u003cem\\u003e/C\\u003c/em\\u003e against time for all of the trials that were conducted with various initial bulk concentrations of pesticides. The values of \\u003cem\\u003ek\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003eapp\\u003c/em\\u003e\\u003c/sub\\u003e can be derived in an easy and straightforward manner by performing a linear regression as given in the Table\\u0026nbsp;\\u003cspan refid=\\\"Tab1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003e. Plot of \\u003cem\\u003e1/k\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003eapp\\u003c/em\\u003e\\u003c/sub\\u003e versus \\u003cem\\u003eC\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003e0\\u003c/em\\u003e\\u003c/sub\\u003e exhibits a linear variation, so validating the Langmuir-Hinshelwood relationship as a description of the initial rates of breakdown. The values of \\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003eR\\u003c/em\\u003e\\u003c/sub\\u003e and \\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003eL\\u0026minus;H\\u003c/em\\u003e\\u003c/sub\\u003e, which were determined separately from the plots.\\u003c/p\\u003e \\u003cp\\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\\u003eRate constants for the photocatalytic degradation of (a) 2,4-D, (b) 4-CPA and (c) TCP removal by pTh-1\\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=\\\"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=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c5\\\" colnum=\\\"5\\\"\\u003e\\u003c/div\\u003e \\u003cthead\\u003e \\u003ctr\\u003e \\u003cth align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eParameter\\u003c/p\\u003e \\u003c/th\\u003e \\u003cth align=\\\"left\\\" colspan=\\\"4\\\" nameend=\\\"c5\\\" namest=\\\"c2\\\"\\u003e \\u003cp\\u003eEffect of concentration for TCP\\u003c/p\\u003e \\u003c/th\\u003e \\u003c/tr\\u003e \\u003c/thead\\u003e \\u003ctbody\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eConcentration (mg/ L)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e10\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e15\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e20\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e25\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003ek\\u003csub\\u003e\\u003cem\\u003eapp\\u003c/em\\u003e\\u003c/sub\\u003e (1/min)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.004\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.003\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.002\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.002\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eRSS\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.005\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e5.97E-04\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e7.89E-04\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.001\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003ePearson's r\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.997\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.999\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.999\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.997\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eR-Square (COD)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.994\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.999\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.998\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.994\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eAdj. R-Square\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.993\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.998\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.997\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.993\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eE\\u003csub\\u003eEO\\u003c/sub\\u003e experimental\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e870400\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e1160533\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1740800\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e1740800\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003ek\\u003csub\\u003eLH\\u003c/sub\\u003e (mg/ L/ min)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colspan=\\\"4\\\" nameend=\\\"c5\\\" namest=\\\"c2\\\"\\u003e \\u003cp\\u003e0.084\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eK\\u003csub\\u003eR\\u003c/sub\\u003e (L/mg)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colspan=\\\"4\\\" nameend=\\\"c5\\\" namest=\\\"c2\\\"\\u003e \\u003cp\\u003e0.068\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u0026nbsp;\\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colspan=\\\"4\\\" nameend=\\\"c5\\\" namest=\\\"c2\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003eEffect of concentration for 2,4-D\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eConcentration (mg/ L)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e10\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e15\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e20\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e25\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003ek\\u003csub\\u003e\\u003cem\\u003eapp\\u003c/em\\u003e\\u003c/sub\\u003e (1/min)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.010\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.009\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.008\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.007\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eRSS\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.055\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.025\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.010\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.014\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003ePearson's r\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.994\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.996\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.998\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.997\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eR-Square (COD)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.989\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.993\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.996\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.994\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eAdj. R-Square\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.987\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.993\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.996\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.993\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eE\\u003csub\\u003eEO\\u003c/sub\\u003e experimental\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e34816\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e386844\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e435200\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e497371\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003ek\\u003csub\\u003eLH\\u003c/sub\\u003e (mg/L/ min)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colspan=\\\"4\\\" nameend=\\\"c5\\\" namest=\\\"c2\\\"\\u003e \\u003cp\\u003e0.302\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eK\\u003csub\\u003eR\\u003c/sub\\u003e (L/mg)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colspan=\\\"4\\\" nameend=\\\"c5\\\" namest=\\\"c2\\\"\\u003e \\u003cp\\u003e0.043\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u0026nbsp;\\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colspan=\\\"4\\\" nameend=\\\"c5\\\" namest=\\\"c2\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003eEffect of concentration for 4-CPA\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eConcentration (mg/L)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e10\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e15\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e20\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e\\u003cb\\u003e25\\u003c/b\\u003e\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003ek\\u003csub\\u003e\\u003cem\\u003eapp\\u003c/em\\u003e\\u003c/sub\\u003e (1/min)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.015\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.012\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.010\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.009\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eRSS\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.027\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.009\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.015\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.013\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003ePearson's r\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.998\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.999\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.998\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.998\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eR-Square (COD)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.997\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.998\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.997\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.996\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eAdj. R-Square\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e0.997\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e0.998\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.996\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e0.996\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eE\\u003csub\\u003eEO\\u003c/sub\\u003e experimental\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e23211\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e29013\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e34816\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e38684\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003ek\\u003csub\\u003eLH\\u003c/sub\\u003e (mg/L/ min)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colspan=\\\"4\\\" nameend=\\\"c5\\\" namest=\\\"c2\\\"\\u003e \\u003cp\\u003e0.284\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003eK\\u003csub\\u003eR\\u003c/sub\\u003e (L/mg)\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colspan=\\\"4\\\" nameend=\\\"c5\\\" namest=\\\"c2\\\"\\u003e \\u003cp\\u003e0.079\\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=\\\"Sec14\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e3.4. Equilibrium studies\\u003c/h2\\u003e \\u003cp\\u003eLangmuir theory states that the adsorption proceeds in a single layer on the surface of adsorbents with homogeneous active sites scattered across its entire surface. An increase in absorption capacity produces an exponential decrease in surface binding energy, generating multilayers from adsorbed ions, according to the Freundlich model (Wang and Guo, 2020). Redlich-Peterson and Sips models are hybrid model of Langmuir and Freundlich models widely used in homogeneous and heterogeneous sorption tests (Wang and Guo, 2020). The fitting of equilibrium experimental data with isotherms for the tested pesticides are shown in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig6\\\" class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003e and model parametric values are given in the Table\\u0026nbsp;\\u003cspan refid=\\\"Tab2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003e. It was noted that the Sips isotherm is followed by equilibrium data for chosen herbicides by the pTh-1 nanocomposites.\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e \\u003cp\\u003e\\u003cstrong\\u003eTable 2\\u0026nbsp;\\u003c/strong\\u003eEquilibrium isotherm constants for (a) 2,4-D, (b) 4-CPA and (c) TCP removal by pTh-1\\u003c/p\\u003e\\n\\u003ctable border=\\\"0\\\" cellpadding=\\\"0\\\" cellspacing=\\\"0\\\"\\u003e\\n \\u003ctbody\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd width=\\\"22.24199288256228%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eIsotherms\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"23.665480427046262%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eParameters\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"18.14946619217082%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eTCP\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"17.793594306049823%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e2,4-D\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"18.14946619217082%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e4-CPA\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd colspan=\\\"5\\\" width=\\\"100%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eLangmuir\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd rowspan=\\\"7\\\" width=\\\"22.24199288256228%\\\"\\u003e\\n \\u003cp\\u003e\\u0026nbsp;\\u0026nbsp; \\u0026nbsp; \\u0026nbsp; \\u0026nbsp; \\u0026nbsp; \\u0026nbsp;\\u0026nbsp;\\u003cimg 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width=\\\"22.88329519450801%\\\"\\u003e\\n \\u003cp\\u003e0.383\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e0.321\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"30.434782608695652%\\\"\\u003e\\n \\u003cp\\u003en\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e2.700\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"22.88329519450801%\\\"\\u003e\\n \\u003cp\\u003e1.986\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e1.472\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"30.434782608695652%\\\"\\u003e\\n \\u003cp\\u003eReduced Chi-Sqr\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e0.015\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"22.88329519450801%\\\"\\u003e\\n \\u003cp\\u003e0.024\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e5.50E-05\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"30.434782608695652%\\\"\\u003e\\n \\u003cp\\u003eR-Square (COD)\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e0.999\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"22.88329519450801%\\\"\\u003e\\n \\u003cp\\u003e0.998\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e0.999\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"30.434782608695652%\\\"\\u003e\\n \\u003cp\\u003eAdj. R-Square\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e0.998\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"22.88329519450801%\\\"\\u003e\\n \\u003cp\\u003e0.997\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e0.999\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"30.434782608695652%\\\"\\u003e\\n \\u003cp\\u003eRSS\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e0.045\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"22.88329519450801%\\\"\\u003e\\n \\u003cp\\u003e0.072\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"23.340961098398168%\\\"\\u003e\\n \\u003cp\\u003e1.65E-04\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003c/tbody\\u003e\\n\\u003c/table\\u003e \\u003c/div\\u003e\\u003cbr/\\u003e\\u003cdiv id=\\\"Sec15\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e3.5. Kinetic studies\\u003c/h2\\u003e \\u003cp\\u003ePseudo-first, pseudo-second, Elovich and intraparticle diffusion models were used to fit the experimental data in order to make a prediction about the removal mechanism (Zhou et al., 2011; Edet and Ifelebuegu, 2020; Yuan et al., 2015). Intra-particle diffusion is another kinetic model used to study the rate of pesticides adsorption on pTh-1 (data not shown). The plots had two separate regions where the first linear trend which indicates external diffusion of pesticides by active sites, spread over the pTh-1\\u0026rsquo;s surface. Each of these regions are represented by the first linear trend. The second linear component represents the intra-particle diffusion by active sites dispersed on the pTh-1 and eventually the development of the equilibrium. Intra-particle diffusion constant, \\u003cem\\u003ek\\u003c/em\\u003e\\u003csup\\u003e\\u003cem\\u003eid\\u003c/em\\u003e\\u003c/sup\\u003e values were obtained from the slope of the second linear portions of the plot of qt versus t\\u003csup\\u003e0.5\\u003c/sup\\u003e for various pesticides concentrations. As can be shown in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig7\\\" class=\\\"InternalRef\\\"\\u003e7\\u003c/span\\u003e, a pseudo-second order kinetic model that provides an appropriate description of the sorption kinetics of both of the targeted pollutants onto pTh-1 is supported by values of \\u003cem\\u003eR\\u003c/em\\u003e\\u003csup\\u003e\\u003cem\\u003e2\\u003c/em\\u003e\\u003c/sup\\u003e that are high and RSS values that are low. In addition, there is only a slight variation between the calculated and experimental values of q\\u003csub\\u003ee\\u003c/sub\\u003e, which further supports the validity of the pseudo-second order model that is presented in Tables\\u0026nbsp;\\u003cspan refid=\\\"Tab3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003e and \\u003cspan refid=\\\"Tab4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003e. A similar observation was reported in a polythiophene-based composite for the adsorption of heavy metals (Arabahmadi and Ghorbani, 2017).\\u003c/p\\u003e \\u003cp\\u003e \\u003c/p\\u003e \\u003cp\\u003e\\u003cstrong\\u003eTable 3\\u0026nbsp;\\u003c/strong\\u003eEstimated parametric values of pseudo-first and pseudo-second order models\\u0026nbsp;\\u003c/p\\u003e\\n\\u003cdiv align=\\\"center\\\"\\u003e\\n \\u003ctable border=\\\"1\\\" cellpadding=\\\"0\\\" cellspacing=\\\"0\\\" width=\\\"102%\\\"\\u003e\\n \\u003ctbody\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd rowspan=\\\"2\\\" width=\\\"13.26530612244898%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eModel\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd rowspan=\\\"2\\\" width=\\\"14.285714285714286%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eParameters\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd colspan=\\\"4\\\" width=\\\"24.489795918367346%\\\"\\u003e\\n 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valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.007\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.001\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.006\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.009\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"11.25%\\\"\\u003e\\n \\u003cp\\u003e1.03E-11\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.005\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.007\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.005\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n 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valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.999\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"11.25%\\\"\\u003e\\n \\u003cp\\u003e1\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.998\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.998\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.999\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd width=\\\"17.5%\\\"\\u003e\\n \\u003cp\\u003eAdj. R-Square\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.998\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.999\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"7.5%\\\"\\u003e\\n \\u003cp\\u003e0.999\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"7.5%\\\"\\u003e\\n \\u003cp\\u003e0.997\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.997\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.999\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.999\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.998\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"11.25%\\\"\\u003e\\n \\u003cp\\u003e1\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.997\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.998\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.998\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd width=\\\"17.5%\\\"\\u003e\\n \\u003cp\\u003eRSS\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.014\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.035\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"7.5%\\\"\\u003e\\n \\u003cp\\u003e0.032\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"7.5%\\\"\\u003e\\n \\u003cp\\u003e0.152\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.037\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.006\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.034\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"bottom\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.045\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"11.25%\\\"\\u003e\\n \\u003cp\\u003e5.13E-11\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.027\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.038\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.25%\\\"\\u003e\\n \\u003cp\\u003e0.026\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003c/tbody\\u003e\\n \\u003c/table\\u003e\\u003cbr/\\u003e\\n\\u003c/div\\u003e\\u003cp\\u003e\\u003cstrong\\u003eTable 4\\u0026nbsp;\\u003c/strong\\u003eEstimated parametric values of Elovich and intra-particle diffusion models\\u0026nbsp;\\u003c/p\\u003e\\n\\u003cdiv align=\\\"center\\\"\\u003e\\n \\u003ctable border=\\\"1\\\" cellpadding=\\\"0\\\" cellspacing=\\\"0\\\" width=\\\"100%\\\"\\u003e\\n \\u003ctbody\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd rowspan=\\\"2\\\" width=\\\"12.371134020618557%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eModel\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd rowspan=\\\"2\\\" width=\\\"15.463917525773196%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eParameters\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd colspan=\\\"4\\\" valign=\\\"top\\\" width=\\\"22.68041237113402%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eTCP (mg/L)\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd colspan=\\\"4\\\" valign=\\\"top\\\" width=\\\"24.742268041237114%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e2,4-D (mg/L)\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd colspan=\\\"4\\\" valign=\\\"top\\\" width=\\\"24.742268041237114%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e4-CPA (mg/L)\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.936507936507937%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e10\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.936507936507937%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e15\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.936507936507937%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e20\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.936507936507937%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e25\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.936507936507937%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e10\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.936507936507937%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e15\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.936507936507937%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e20\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.936507936507937%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e25\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"11.11111111111111%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e10\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.936507936507937%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e15\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.936507936507937%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e20\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"9.523809523809524%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003e25\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd colspan=\\\"14\\\" width=\\\"NaN%\\\"\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eElovich\\u003c/strong\\u003e\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd rowspan=\\\"6\\\" width=\\\"13.333333333333334%\\\"\\u003e\\n \\u003cp\\u003e\\u0026nbsp;\\u003cimg src=\\\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAH8AAABjCAYAAACyqd/zAAAHU0lEQVR4nO2dP2gTbRzHv3l5N1MCPh0sQZBAk62txBSUTL2lVQcRXC+DVMUlRdvBpQQnh7OmgjhIxbpEySLE6CAWqllzlWy9QB3kkiwRw92m8HuHvndv/l+atEnee54P3JDL5bnnfp97nnue33OlHiIiCLjkr1FXQDA6hHyOEfI5RsjnGCGfY4R8jhHyOUbI5xghn2OEfI4R8jlGyOcYIZ9jhHyOEfI5RsjnGCGfY4R8jhHyOUbI5xghn2OEfI4R8jlGyOcYIZ9jXCvfNE08efIEoVAIjx8/HnV1xpK/R12Bk8A0Tdy8eROfP39GtVoddXXGFle2fK/Xi7dv3+LTp09gjI26OmOLK+ULekPI5xghn2OEfI4R8jlGyOcYIZ9jhPw6rKzg/Pw8yuVyX2Xs7e1hbW0Npmkee70mJyfh8Xjg8Xhw69atlnOYpom1tTUUi8XeCqYhsbu7S6qqDut0JMsyAbC3QCBApVKp628ymUzPx7YjlUrR4uIiaZrWb7VbKJVKFIlESJIku9xsNkuMMZJluSWuqqrSpUuXKJVKOZY9NPmJRKKvgA4bWZb7kp/JZCgSiRz7NcqyTJIkkWEY9r5SqUSBQIBkWW4bV+v7TCbTteyhdPtv3rzB169fMTExMYzTDZ1yuYx4PI719XVMTU0dW7l7e3vIZrNYWVmB1+u191cqFdRqNXi93rZxnZqawubmJuLxePfH16B3pqZpFIlECAApikKKotgtx+qyUNf9Ot2No6a+5ZfLZbp37x5FIhHSNI2Wl5cJQEsLVxSlpXW2Q9M0WlxcJADEGLNjYbVURVEajq+PpYVhGCRJEp0+fbprXK3jmsusZyD5mUyGGGOUSCTIMAzKZrMUDAYbAmFVYtylW1jyNU0jSZJsURsbG2QYBqmqaj9vif67PutzJxRFIQD2s1hVVfsmate115drGAbJskyMMQoGg6QoSk9xbVduPX3Lbw4CUfs7WFVVCgaDXQd7zYOzdptTcI+L5md+8+dm2VYcukmwBpLNrTCRSNDDhw+JMdYSn07lWg3u5cuXjnFVFKVt2RZ9PfOtKYXP58OjR4/s/fl8HrVaDQsLC/Y+Xddx9uxZTE9Pdyxve3sbdHgjdty2t7f7qeqJo+t613cGrPGAJEm4fft2w3derxfr6+u4cuUKzp8/3/Ddzs4OfD4fwuFww/5wOAyfz4enT586xjUUCqFarULX9bbf9yW/WCzi27dvuHv3bsMAJ51OY25urqFC6XQafr+/YcDCE/l8HgcHB1haWmqJQaFQQCAQaGhAwGHj+vjxI6LRaMcB5K9fvwaOa1/yd3Z2AKChhVsj0/oKmaYJXddx48aNruXFYjE7edFpi8ViHX/v9Ntu20mTTqfBGGuIFQC8f/8er1+/xubmZotgq3G1i1s+n8fPnz9x6tQpx7g60fdUz+fz4cyZMwAOJT9//hwAGipULBbx48cP+P3+rmUN2u07/bbbNih+vx+MMezv73c8pj5WwGFc4vE4AoFAS7cOAMlksm2Xb5omkskkZmdn8fv3b8e47u/vgzHW8bi+5IdCIdRqNVQqFZimia2tLczPz7dUWNd1/PnzBwCwtbXVz6mGitVTdfoMAIZh4Pv379B1HaZpYnp6GnNzcygUCm3LnJmZwcHBAXZ3dwEAHz58wMWLFyFJEi5cuIBKpQLgMBfy5csXlMtl5HI51Go1KIpip3CLxSIWFhYwOzuLO3fu9BTXQqHQ8hhuoONQsQvWiBcALS8v21OR5mmFNTK1pknjjjUdA0DXr1+3rxH/pnxVVaVAIGDvs6632zzfMAw7PwCAgsGgPd1LpVLEGCPGmL3PmhmkUil68eIFMcbs3EI2m7WPcYrric/zj3IiN9NrOrUX+k0vN5PJZBzLORb5vczl3U4vwXaiPmc/CL3ejAPL79TljwuGYdDGxobdfdY/qo4bqxvvtxFY3fkgjchKIZ/4ql79M9J6Lo7Typ3TcuhJoGkara6uHvnm6jVN7FTG6upqzzePh8i9/2ApFotB13W8e/fOzj2Uy2VEo1FEo9GxzRoOC1f+uRbwX9Lp1atXbZdDB02QuAHXvsbVLjdurUk8ePAAV69eHWHtxgNXyq/PjU9MTCAWi2FychLhcBhLS0u4f//+qKs4HvQ9uhhjnJZDeZ6S1uPKlu+0HJpMJkdUs/HCdfJ7WQ6dmZkZcq3GE9fJd1oObX7ZhGdcJ99pObTdWzO84ir5vSyHPnv2bMS1HB9cleSxXplKpVIwTRPnzp1DtVpFJBJBIpHA5cuXR13FscJV6d1YLIZcLodcLnesfzzhVlzT7VtdfrdRvqAR18i3RvIrKyujrsr/Bld0+6Zp4tq1a/D7/dyv1B0FV8gX9Idrun3B0RHyOUbI5xghn2OEfI4R8jlGyOcYIZ9jhHyOEfI5RsjnGCGfY4R8jhHyOUbI5xghn2OEfI4R8jlGyOcYIZ9jhHyOEfI5RsjnGCGfY4R8jhHyOUbI5xghn2OEfI4R8jnmH6xkA7o+FvcXAAAAAElFTkSuQmCC\\\"\\u003e\\u003c/p\\u003e\\n 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valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e1.303\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.357\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.544\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.615\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.975\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"18.9873417721519%\\\"\\u003e\\n \\u003cp\\u003eReduced Chi-Sqr\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.228\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.707\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.910\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e1.079\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.060\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.214\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.706\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e1.286\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.162\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.241\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.331\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.709\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"18.9873417721519%\\\"\\u003e\\n \\u003cp\\u003eR-Square (COD)\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.934\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.927\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.922\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.921\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.982\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.972\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.929\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.878\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.936\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.925\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.931\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.878\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"18.9873417721519%\\\"\\u003e\\n \\u003cp\\u003eAdj. R-Square\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.921\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.912\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.907\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.905\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.978\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.966\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.915\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.854\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.923\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.910\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.917\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.854\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003ctr\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"18.9873417721519%\\\"\\u003e\\n \\u003cp\\u003eRSS\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e1.142\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e3.538\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e4.552\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e5.397\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e0.300\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e1.072\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e3.531\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e6.434\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e0.812\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e1.205\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"6.329113924050633%\\\"\\u003e\\n \\u003cp\\u003e1.659\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003ctd valign=\\\"top\\\" width=\\\"7.594936708860759%\\\"\\u003e\\n \\u003cp\\u003e3.548\\u003c/p\\u003e\\n \\u003c/td\\u003e\\n \\u003c/tr\\u003e\\n \\u003c/tbody\\u003e\\n \\u003c/table\\u003e\\n\\u003c/div\\u003e \\u003c/div\\u003e \\u003cbr/\\u003e\\u003cdiv id=\\\"Sec16\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e3.6. Mechanism of 2,4-D, 4-CPA and TCP degradation\\u003c/h2\\u003e \\u003cp\\u003eWhen the irradiation energy is higher than the band gap of TiO\\u003csub\\u003e2\\u003c/sub\\u003e, the photocatalytic oxidation takes place, which results in the creation of electrons and holes. The absorption of hydroxyl groups on the pTh-1\\u0026rsquo;s surface, which oxidizes the organic molecules and initiates photocatalytic oxidation. As a result, the rate-limiting phase in this process has been thought to be the surface reaction (Vishnuganth et al., 2016). According to Boden-stein theory, at steady state the concentration of hydroxyl radicals and H\\u003csup\\u003e+\\u003c/sup\\u003e ions will remain unchanged. Deformation of organic complexes in the system may be traced back to the formation of OH radical, which occurred when H\\u003csup\\u003e+\\u003c/sup\\u003e and OH\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e ions combined to create an electron hole pair (Vishnuganth et al., 2016).\\u003cdiv id=\\\"Equ5\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ5\\\" name=\\\"EquationSource\\\"\\u003e\\n$$Pesticides+{pTH}_{1}\\\\leftrightarrows {\\\\left(Pesticides-{pTH}_{1}\\\\right)}_{adsorb}\\\\to {(Herbicides-{TiO}_{2})}_{adsorb}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e5\\u003c/div\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Equ6\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ6\\\" name=\\\"EquationSource\\\"\\u003e\\n$${TiO}_{2}+hv\\\\to \\\\left({TiO}_{2}\\\\right){e}^{-}+{h}^{+}+Heat$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e6\\u003c/div\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Equ7\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ7\\\" name=\\\"EquationSource\\\"\\u003e\\n$${h}^{+}+{H}_{2}O\\\\to {H}^{+}+{OH}^{.}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e7\\u003c/div\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Equ8\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ8\\\" name=\\\"EquationSource\\\"\\u003e\\n$${e}^{-}+\\\\frac{1}{2}{O}_{2}+{H}^{+}\\\\to {OH}^{.}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e8\\u003c/div\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Equ9\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ9\\\" name=\\\"EquationSource\\\"\\u003e\\n$${OH}^{.}+{\\\\left(Pesticides-{TiO}_{2}\\\\right)}_{adsorb}\\\\underrightarrow{hv/{TiO}_{2}}{\\\\left({H}_{i}-{TiO}_{2}\\\\right)}_{adsorb}\\\\to {H}_{i}+{TiO}_{2}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e9\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e \\u003cp\\u003eIn most cases, the photocatalytic process could not be started until after the adsorption-desorption equilibrium had been established. As a result, it is possible to propose the equilibrium conditions described by the following equations.\\u003cdiv id=\\\"Equ10\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ10\\\" name=\\\"EquationSource\\\"\\u003e\\n$${K}_{+1}C\\\\left(1-{⍕}_{pesticides}-\\\\sum {\\\\text{⍕}}_{i}-{\\\\text{⍕}}_{{TiO}_{2}}\\\\right)={K}_{1}\\\\text{⍕}{TiO}_{2}+{K}_{-1}{\\\\text{⍕}}_{pesticides}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e10\\u003c/div\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Equ11\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ11\\\" name=\\\"EquationSource\\\"\\u003e\\n$${K}_{+I}{C}_{i}\\\\left(1-{⍕}_{pesticides}-\\\\sum {\\\\text{⍕}}_{i}-{\\\\text{⍕}}_{{TiO}_{2}}\\\\right)={K}_{-i}\\\\text{⍕}{TiO}_{2}+{K}_{-1}{\\\\text{⍕}}_{pesticides}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e11\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e \\u003cp\\u003ewhere pesticides refer to TCP, 4-CPA and 2,4-D respectively; \\u003cem\\u003ehv\\u003c/em\\u003e is the photon energy from UV light; \\u003cem\\u003eh\\u003c/em\\u003e\\u003csup\\u003e\\u003cem\\u003e+\\u003c/em\\u003e\\u003c/sup\\u003e and \\u003cem\\u003ee\\u003c/em\\u003e\\u003csup\\u003e\\u003cem\\u003e\\u0026minus;\\u003c/em\\u003e\\u003c/sup\\u003e refers to the holes and electrons; ⍕\\u003csub\\u003epesticides\\u003c/sub\\u003e and ⍕TiO\\u003csub\\u003e2\\u003c/sub\\u003e are the fractional coverage of the pesticides and TiO\\u003csub\\u003e2\\u003c/sub\\u003e on pTH-1\\u0026rsquo;s surface respectively. \\u003cem\\u003eC\\u003c/em\\u003e and \\u003cem\\u003eC\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003ei\\u003c/em\\u003e\\u003c/sub\\u003e are the concentration of pesticides and intermediates (mg/L) whereas \\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003e+\\u0026thinsp;1\\u003c/em\\u003e\\u003c/sub\\u003e and \\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/em\\u003e\\u003c/sub\\u003e rate constants of adsorption and desorption, respectively. When the aforementioned process is taken into consideration, it is pertinent to assert that the photocatalytic degradation owing to the oxidizing of intermediate products by the OH radicals present on the pTh-1\\u0026rsquo;s surface (Zhang et al., 2011).\\u003c/p\\u003e \\u003c/div\\u003e \\u003cdiv id=\\\"Sec17\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e3.7. Energy consumption and economic analysis\\u003c/h2\\u003e \\u003cp\\u003ePhotocatalysis of pesticides is one that requires a significant amount of electrical energy and accounts for a significant portion of the overall operating costs (Cater et al., 2000; Vishnuganth et al., 2016). E\\u003csub\\u003eEO\\u003c/sub\\u003e may be determined for a batch type reactor by utilizing the equation that is shown below (Daneshvar et al., 2005);\\u003cdiv id=\\\"Equ12\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ12\\\" name=\\\"EquationSource\\\"\\u003e\\n$${E}_{E0}=\\\\frac{P\\\\times t\\\\times 1000}{V\\\\times 60\\\\times log\\\\left(\\\\frac{{C}_{0}}{{C}_{f}}\\\\right)}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e12\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e \\u003cp\\u003eThe preceding equation has an implied connection to the L-H model's first order kinetics as follows:\\u003cdiv id=\\\"Equ13\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ13\\\" name=\\\"EquationSource\\\"\\u003e\\n$$ln\\\\left(\\\\frac{{C}_{0}}{{C}_{t}}\\\\right)={k}_{obs}t$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e13\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e \\u003cp\\u003eBy combining the above equations, E\\u003csub\\u003eEO\\u003c/sub\\u003e can be expressed as;\\u003cdiv id=\\\"Equ14\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ14\\\" name=\\\"EquationSource\\\"\\u003e\\n$${E}_{E0}=\\\\frac{P\\\\times 38.4}{V\\\\times {k}_{obs}t}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e14\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e \\u003cp\\u003eEq.\\u0026nbsp;(\\u003cspan refid=\\\"Equ14\\\" class=\\\"InternalRef\\\"\\u003e14\\u003c/span\\u003e) are used for determining the amount of electrical energy required to complete one order in an idealized batch reactor. The experimental results for determining E\\u003csub\\u003eEO\\u003c/sub\\u003e for the elimination of pesticides using the pTh-1 photocatalysis system are presented in Table\\u0026nbsp;\\u003cspan refid=\\\"Tab5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003e. Value of E\\u003csub\\u003eEO\\u003c/sub\\u003e increased with raise in the pesticide\\u0026rsquo;s concentrations (Cater et al., 2000; Vishnuganth et al., 2016). The fact that the value of E\\u003csub\\u003eEO\\u003c/sub\\u003e from the kinetic model matches with the value from the experimental data describing that the process followed first-order kinetics.\\u003c/p\\u003e \\u003cp\\u003e \\u003cdiv class=\\\"gridtable\\\"\\u003e\\u003ctable float=\\\"Yes\\\" id=\\\"Tab5\\\" border=\\\"1\\\"\\u003e \\u003ccaption language=\\\"En\\\"\\u003e \\u003cdiv class=\\\"CaptionNumber\\\"\\u003eTable 5\\u003c/div\\u003e \\u003cdiv class=\\\"CaptionContent\\\"\\u003e \\u003cp\\u003eCost estimates for the removal of TCP, 2,4-D and 4-CPA by pTh-1\\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=\\\"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=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c5\\\" colnum=\\\"5\\\"\\u003e\\u003c/div\\u003e \\u003cthead\\u003e \\u003ctr\\u003e \\u003cth align=\\\"left\\\" colname=\\\"c1\\\"\\u003e \\u003cp\\u003ePesticides\\u003c/p\\u003e \\u003c/th\\u003e \\u003cth align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003eConcentration (mg/L)\\u003c/p\\u003e \\u003c/th\\u003e \\u003cth align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003epH\\u003c/p\\u003e \\u003c/th\\u003e \\u003cth align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003eCatalyst load (g/L)\\u003c/p\\u003e \\u003c/th\\u003e \\u003cth align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003eCost ₹/kg removal\\u003c/p\\u003e \\u003c/th\\u003e \\u003c/tr\\u003e \\u003c/thead\\u003e \\u003ctbody\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\" morerows=\\\"7\\\" rowspan=\\\"8\\\"\\u003e \\u003cp\\u003eTCP\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.3\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e60,678\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e15\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.3\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e50,695\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e20\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.3\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e40,644\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e25\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.3\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e34,923\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e7.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e1,00,312\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e8.8\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e2,04,986\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.3\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.5\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e1,00,312\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.3\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.5\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e69,333\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\" morerows=\\\"7\\\" rowspan=\\\"8\\\"\\u003e \\u003cp\\u003e2,4-D\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.9\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e54,822\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e15\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.9\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e39,786\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e20\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.9\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e30,615\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e25\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.9\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e25,834\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e8.2\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e76,043\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e10.8\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e5,23,852\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.9\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.5\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e76,043\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.9\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.5\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e56,127\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c1\\\" morerows=\\\"7\\\" rowspan=\\\"8\\\"\\u003e \\u003cp\\u003e4-CPA\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.8\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e51,810\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e15\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.8\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e37,869\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e20\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.8\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e29,727\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e25\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.8\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e25,145\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e6.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e57,182\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e9.3\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.0\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e61,071\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.8\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e0.5\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e60,803\\u003c/p\\u003e \\u003c/td\\u003e \\u003c/tr\\u003e \\u003ctr\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e \\u003cp\\u003e10\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e \\u003cp\\u003e4.8\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c4\\\"\\u003e \\u003cp\\u003e1.5\\u003c/p\\u003e \\u003c/td\\u003e \\u003ctd align=\\\"left\\\" colname=\\\"c5\\\"\\u003e \\u003cp\\u003e55,078\\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\\u003eThe sum of capital, operational and maintenance expenses are used to calculate the total costs, which is dependent on the type of pollutant, its concentration and the reactor, designs. Because of this, the evaluation of the costs was predicated on the figure-of-merit (E\\u003csub\\u003eEO\\u003c/sub\\u003e) that was computed for each individual batch of experimental runs (Esplugas et al., 2002; Remya and Lin 2011). Operating cost (total) under optimum circumstances such as pTh-1 load, pesticide concentration, pH, reaction time with constant UV intensity were calculated using the following relations;\\u003cdiv id=\\\"Equ15\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ15\\\" name=\\\"EquationSource\\\"\\u003e\\n$$Operating cost \\\\left(₹/kg\\\\right)=\\\\frac{Energy consumed \\\\left(kWh\\\\right)\\\\times unit cost (₹/kWh)\\\\times {10}^{6}}{pesticide removal \\\\left(mg\\\\right)}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e15\\u003c/div\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Equ16\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ16\\\" name=\\\"EquationSource\\\"\\u003e\\n$$Energy consumed \\\\left(kWh\\\\right)=\\\\frac{Power input \\\\left(kW\\\\right)\\\\times Reaction time \\\\left(min\\\\right)}{1000\\\\times 60}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e16\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e \\u003cp\\u003eTable\\u0026nbsp;\\u003cspan refid=\\\"Tab5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003e is a tabulation of the total operating cost that is required for the removal of one kilogram of pesticides from contaminated water and inputs considered for cost calculation is provided in the Supplementary Materials Experimental S3. It was noticed that the total operating cost, expressed in terms of rupees per kilogram, decreases in proportion to increases in the initial pesticide concentration (Asha et al., 2015).\\u003c/p\\u003e \\u003c/div\\u003e \\u003cdiv id=\\\"Sec18\\\" class=\\\"Section2\\\"\\u003e \\u003ch2\\u003e3.8. Reusability of pTh-1\\u003c/h2\\u003e \\u003cp\\u003eReuse of an adsorbent or catalyst is what affects the practical viability and the cost of a treatment approach from a technological and economic perspective. Within the scope of this investigation, pTh-1\\u0026rsquo;s reusability was investigated by carrying out five consecutive photodegradation cycles in ideal conditions. Recovered composite was washed, dried at 70\\u0026deg;C prior being employed in the next cycle. After five consecutive cycles, the photo-degradation efficiency of pTh-1 declined from, 86 to 79%, 91.6 to 83% and 78 to 70% during the removal of 2,4-D, 4-CPA and TCP as shown in the Supplementary Materials Figure S4. Results of the reusability tests indicate that the pTh-1 material has a substantial repeatability, although there is a slight decrease in photo-degradation after three-cycles of operations. This could be attributed to particle aggregation during catalysis or catalyst loss while recovering, but the decrease is still relatively small (Li et al., 2008; Rathod et al., 2018).\\u003c/p\\u003e \\u003c/div\\u003e\"},{\"header\":\"4. Conclusions\",\"content\":\"\\u003cp\\u003eIn this study, we have described the production of a functionalized pTh-TiO\\u003csub\\u003e2\\u003c/sub\\u003e nanocomposites using oxidative polymerization using different proportions of TiO\\u003csub\\u003e2\\u003c/sub\\u003e. pTh-1 nanocomposite exerted better removal efficiencies when compared with other materials and was able to adsorb with concomitant photocatalytic breakdown of three distinct pesticides within 120 min. The different sorption equilibria, kinetics were evaluated for the removal of 2,4-D, 4-CPA and TCP using empirical models. While L-H model described the removal of pesticides using pTH-1 through photo-degradation. Conclusively, the reusability of the nano-composites and process economics for the pesticide removal were evaluated.\\u003c/p\\u003e\"},{\"header\":\"Declarations\",\"content\":\"\\u003cp\\u003e\\u003cstrong\\u003eEthical approval and consent to participate:\\u003c/strong\\u003e The authors declare that they have no known competing financial interests or personal relationships that seem to affect the work reported in this article.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eConsent for Publication:\\u003c/strong\\u003e We do not have any individual person\\u0026rsquo;s data in any form.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eAvailability of data and materials:\\u003c/strong\\u003e Not applicable\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eCompeting interest:\\u003c/strong\\u003e The authors declare that they have no conflict of interest.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eFunding:\\u003c/strong\\u003e Not applicable\\u0026nbsp;\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eAuthors\\u0026rsquo; contribution\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003ePareshkumar G Moradeeya: Investigation and writing-original draft. Madhava Anil Kumar: Conceptualization, writing-original draft. Archana Sharma: review and editing. Shaik Basha: Supervision, Writing-Review \\u0026amp; Editing. All authors read and approved the manuscript.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eAcknowledgement\\u0026nbsp;\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eThe authors would like to extend their gratitude to the Director of CSIR-NEERI and Director of CSIR-CSMCRI, as well as the Management of Marwadi University, for the help they have provided. The manuscript has been given the reference number CSIR-NEERI/KRC/2022/JUNE/HZC/1.\\u003c/p\\u003e\"},{\"header\":\"References\",\"content\":\"\\u003col\\u003e\\u003cli\\u003e\\u003cspan\\u003eAlalm MG, Tawfik A, Ookawara S (2015) Comparison of solar TiO\\u003csub\\u003e2\\u003c/sub\\u003e photocatalysis and solar photo-Fenton for treatment of pesticides industry wastewater: operational conditions, kinetics, and costs. 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Catal Sci Technol 11, 6630\\u0026ndash;6648. https://doi.org/10.1039/D1CY01129D\\u003c/span\\u003e\\u003c/li\\u003e\\u003c/ol\\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\":\"info@researchsquare.com\",\"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\":\"Degradation, 2,4-dichlorophenoxyacetic acid, Triclopyr acid, Polythiophene, TiO2, 4-Chlorophenoxyacetic acid\",\"lastPublishedDoi\":\"10.21203/rs.3.rs-1839933/v1\",\"lastPublishedDoiUrl\":\"https://doi.org/10.21203/rs.3.rs-1839933/v1\",\"license\":{\"name\":\"CC BY 4.0\",\"url\":\"https://creativecommons.org/licenses/by/4.0/\"},\"manuscriptAbstract\":\"\\u003cp\\u003eAn integrated process involving adsorption and photocatalysis are utilized for the breakdown of three different pesticides such as 2,4-D, 4-CPA and TCP. Photo-catalysts were fabricated using polythiophene supported TiO\\u003csub\\u003e2\\u003c/sub\\u003e composites and utilized for the pesticides degradation under UV light irradiation. The synthesized materials were characterized for elemental, microscopic, spectroscopic and spectrophotometric properties. The outcome shows that polythiophene supported titanium dioxide systems can successfully facilitate the breakdown of pesticides under UV irradiation. The photocatalytic effectiveness of the TiO\\u003csub\\u003e2\\u003c/sub\\u003e catalyst was significantly improved by the addition of polythiophene. Maximum amount of adsorption capacity for 2,4-D, 4-CPA and TCP were 8.18, 6.333, and 9.681 mg/g by pTh-1. The modified version of the Langmuir-Hinshelwood (L-H) model explained the inter-relationship between the adsorption and photodegradation. Results explained that the pTh-1 catalyzed photodegradation of 4-CPA, TCP and 2,4-D exists the surface reaction which was rate-limiting. Langmuir- Hinshelwood and electrical energy per order (E\\u003csub\\u003eEO\\u003c/sub\\u003e) model provided good fit with batch-mode experiments. Furthermore, these models were successful in elucidating the mechanisms of photocatalytic degradation when pTh-1 was available in the reaction mixture.\\u003c/p\\u003e\",\"manuscriptTitle\":\"Sorption-photocatalysis of structurally distinct pesticides using polythiophene/TiO2 composites: Kinetics, equilibrium, reusability and operational economics\",\"msid\":\"\",\"msnumber\":\"\",\"nonDraftVersions\":[{\"code\":1,\"date\":\"2022-08-09 18:03:17\",\"doi\":\"10.21203/rs.3.rs-1839933/v1\",\"editorialEvents\":[{\"type\":\"communityComments\",\"content\":0}],\"status\":\"published\",\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"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\":\"e94291f2-d2b7-42a7-9059-813fb4205287\",\"owner\":[],\"postedDate\":\"August 9th, 2022\",\"published\":true,\"recentEditorialEvents\":[],\"rejectedJournal\":[],\"revision\":\"\",\"amendment\":\"\",\"status\":\"posted\",\"subjectAreas\":[],\"tags\":[],\"updatedAt\":\"2022-10-20T21:25:14+00:00\",\"versionOfRecord\":[],\"versionCreatedAt\":\"2022-08-09 18:03:17\",\"video\":\"\",\"vorDoi\":\"\",\"vorDoiUrl\":\"\",\"workflowStages\":[]},\"version\":\"v1\",\"identity\":\"rs-1839933\",\"journalConfig\":\"researchsquare\"},\"__N_SSP\":true},\"page\":\"/article/[identity]/[[...version]]\",\"query\":{\"redirect\":\"/article/rs-1839933\",\"identity\":\"rs-1839933\",\"version\":[\"v1\"]},\"buildId\":\"J0_U0BvcaRcwD8yVFaRlm\",\"isFallback\":false,\"isExperimentalCompile\":false,\"dynamicIds\":[84888],\"gssp\":true,\"scriptLoader\":[]}","source_license":"CC-BY-4.0","license_restricted":false}