Synthesis and characterization of chitosan-fruit peel nanocomposite with photocatalytic degradation from Tirupur industry dyes

J. Bio. & Env. Sci. 20 2 3 75 | Bhuvaneswari et al. RE RERE RESEARCH SEARCHSEARCH SEARCH PAPER PAPERPAPER PAPER OPEN ACCESS OPEN ACCESSOPEN ACCESS OPEN ACCESS Synthesis and characterization of chitosan-fruit peel nanocomposite with photocatalytic degradation from Tirupur industry dyes P . Bhuvaneswari 1 , S . Amutha 2 , S . Vignesh 2 , M . Sivakavinesan 2 , T . Shanmugavadivu 1 , G. Annadurai 2 , E. Pushpalakshmi 2 , S. Rajaduraipandian 1 , E. Sindhuja *1 1 Department of Chemistry, Sri Paramakalyani College, Manonmaniam Sundaranar University, Alwarkurichi, Tamil Nadu, India 2Sri Paramakalyani Centre of Excellence in Environmental Sciences, Manonmaniam Sundaranar University, Alwarkurichi, Tamil Nadu, India Article published on July 13, 2023 Key words: Photodegradation, Chitosan - fruit peel nanocomposite, Fruit synthesis, Degradation , Dye Abstract The high surface area-to-volume ratio of chitosan-fruit-peel nanocomposite and other distinctive physical, chemical, and biological properties that arise due to its size effects have attracted significant attention in the field of environmental remediation. Wet chemical techniques are commonly used to create metallic nanoparticles; however, the chemicals used are typically dangerous and combustible. Because it doesn't involve the use of hazardous chemicals, the synthesis of nanoparticles using a range of fruit resources is regarded as green technology. Utilizing the powdered peels of Garcina mangostana (mangosteen), the chitosan-fruit peel nanocomposite was created. By employing Fourier spectroscopy (FTIR), X-ray diffractometer (XRD), Field Emission Scanning Electron Microscopy (FESEM), and Thermogravimetric Analysis (TG/DTA), researchers were able to characterize the synthesized chitosan-fruit peel nanocomposite. Chitosan-fruit peel nanocomposite is used to investigate the photocatalytic degradation of model dye and industrial effluent. The sequestration of dye from aqueous solutions using chitosan-fruit peel nanocomposite is the main emphasis of this work. The Chitosan-Fruit Peel Nanocomposite could therefore be a viable adsorbent material in environmental rehabilitation and remediation. * Corresponding Author: E. Sindhuja  [email protected] Journal of Biodiversity and Environmental Sciences (JBES) ISSN: 2220-6663 (Print) 2222-3045 (Online) Vol. 23, No. 1, p. 75-86, 2023 http://www.innspub.net J. Bio. & Env. Sci. 20 2 3 76 | Bhuvaneswari et al. Introduction India is well known for its high-quality textile items and has established itself as the major source of all high-end textile products. From India, clothing is exported to practically the entire developed world. Textiles and apparel account for 30% of India's exports, making them one of the major exporters (Smefdp-Sidbi, 2009). The greatest provider of services in India is the textile industry, which contributes 3% of the GDP. In Tamilnadu, they are concentrated in Tiruppur and Karur, Punjab's Ludhiana, and Gujarat's Surat (Ranganathan et al., 2007). According to Harvey (2008), the textile industry uses a lot of water and generates a lot of wastewater. The demand for textile products grows together with the production of textile wastewater, making the textile sector the primary cause of serious pollution issues on a global scale (Marimuthu et al., 2015). If not properly treated, these effluents pose a serious hazard to human health and the environment since they contain a variety of chemicals and dyes, some of which are nonbiodegradable and carcinogenic (Khehra et al., 2006). The site becomes unusable for further construction as a number of harmful chemicals accumulate there. The effluent-containing dyes are a significant cause of water contamination. According to Kumar et al. (2007), the wastewater produced by various textile mill production processes has high pH, temperature, detergents, oil, suspended and dissolved solids, leveling agents, hazardous and non-biodegradable matter, color, and alkalinity. The primary refractory organics, pigments, toxicants, and surfactants in textile wastewater are chlorinated compounds (AOX). According to Talarposhti et al. (2001), the chemical oxygen demand (COD), biochemical oxygen demand (BOD), pH, and color of textile wastewater are just a few of the many factors that fluctuate. According to (Alexander et al., 2016), the purple mangosteen (Garcinia mangostana), also known simply as mangosteen, is a tropical evergreen tree that is thought to have its origins in the Indonesian islands of Sunda and the Moluccas. Surface water and groundwater are combined to determine the textile industry's water requirements in Tiruppur. Groundwater is used by the plants in Tiruppur alone on an annual basis to the tune of 28.8 billion liters. Water is transported in transporters from nearby towns like Avinashi, Rayapuram, Murugampaliyam, and some locations in the neighboring Erode district. It is unnecessary to mention that Tiruppur has a simple water scarcity. Approximately 80% of the overall water demand is met by transporters. According to Sami et al. (2017), the textile units purchase water at a cost of Rs. 250– 450 per transporter (12,000 liters capacity). In this study, textile dye factories were taken out of an industrial aqueous solution using chitosan-fruit peel (mangosteen), which was used as a low-cost adsorbent. Investigated is how pH, dosages, and dye concentration affects degradation effectiveness. Through degradation tests, the reusability of the chitosan-fruit peel nanocomposite is evaluated. We were able to forecast the number of active sites engaged in the degradation of the pollutants to a thorough physicochemical analysis of our system and the management of the synthesis parameters, which were then compared with experimental adsorption data. Materials and methods Chitosan, which was obtained from crab shells bought at the Tirunelveli Fish Market, was combined with the following analytical-grade chemicals: hydrochloric acid, sodium hydroxide, ceric ammonium nitrate, methyl methacrylate, acrylic acid, sodium thiosulfate, manganese sulfate, sodium iodide, starch, potassium bromide, and nutrient agar. Wastewater from nearby textile dye factories was also used for the analysis. Sample collection and water quality analysis Water samples were taken in Tirupur, Tamil Nadu at three different places. Rayapuram industrial effluent water, Anaipalayam industrial effluent water, and the Noyyal river basin were collected the samples. Before noon, all water samples are collected and kept in clean BOD bottles and 5-liter bottles for water quality analysis. Corazol T blue (0.1g) was dissolved in J. Bio. & Env. Sci. 20 2 3 77 | Bhuvaneswari et al. double-distilled water (100ml) and diluted to different concentrations (0.01g, 0.02g, and 0.03g) to create the solution. Preparation of Chitosan Waste spanner crab shells from regional restaurant suppliers were gathered in Tirunelveli. The shells were cleaned in deionized water and let to dry in the sun for 24 hours. The dried shells were broken down to 50-mesh particle size. Direct usage of 50-mesh crab shells was made for bio-sorption tests. Through a variety of chemical processes, including demineralization, deproteinization, deacetylation and decolorization, chitosan was removed from crab shells. The ground shells were demineralized by refluxing 5% HCl w/w over a period of 6 hours at room temperature. The resulting solid was vacuum filtered after being dried and rinsed with deionized water until the pH was neutral. The resulting solid was deproteinized using a 5% NaOH solution, and the mixture was agitated at 80 o C for 6 hours with a solid/solvent ratio of 1:10 (w/v). The residue was once more cleaned, filtered, and allowed to dry for 48 hours at room temperature. Deacetylation was carried out at 120 o C for 24 hours using a solid/solvent ratio of 1:10 (w/v) and 45% NaOH. The resultant chitosan underwent a 6-hour process of sun drying to remove color. The chitosan nanoparticles were made using the obtained chitosan. The creation of chitosan from crab shells was investigated (Cadogan et al., 2014a). Preparation of chitosan nanocomposite 2g of chitosan were dissolved in 98ml of a 1% acetic acid solution to create a 2% chitosan solution. Chitosan nanoparticles were created using the inotropic gelation method (Shu and Zhu, 2001). After stirring through the N 2 gas for 20 minutes at room temperature, 2 g of dry fruit peel powder, 0.1 g of ceric ammonium nitrate, 1ml of methyl methacrylate, 1ml of acrylic acid, and starch were added to the chitosan solution. The N 2 -treated chitosan nanocomposite solution was heated to 80 o C in a water bath for 24 hours before being air dried. Then used grained to obtain the particles. These dried chitosan fruit peel nanocomposites were utilized for dye adsorption experiments after being cleaned with deionized water. The creation of a nanocomposite was depicted in studies (Cadogan et al., 2014b). Photocatalytic degradation of dyestuff The effect of the different adsorbent dosages was (0.5 to 1.5 g L -1 ) on the dye concentration (0.3g/L). Effect of varied pH values (4, 7.5, and 9) at constant on the dye concentration (0.3g/L) and adsorbent concentrations (0.1 g L -1 ) were studied. Using an Elico pH meter, the pH was adjusted by adding 0.1 M HCL and NaOH. A control setup was also kept going without any adsorbent addition. The suspensions were kept at room temperature in photocatalytic equipment before being exposed to radiation. Aliquots of 3ml solutions were filtered and utilized to assess the photocatalytic degradation of dye at the predetermined time interval. Following this, the absorbance spectrum of the supernatant was determined using UV-Vis spectra at 381nm for model dye and industrial dye adsorption, 382nm (Noyyal river sample and Rayapuram industry effluent water, and 476nm (Anaipalayam industry effluent water. Result and discussion Fourier transforms infrared spectroscopy (FT-IR) analysis The presence of a potential functional group for the production of chitosan nanoparticles is determined via FTIR analysis. Chitosan nanoparticles produced using green manufacturing techniques are reduced and stabilized as a result of these functional groups (Fig. 1). The prominent and broad peak in the 3500– 3300 range in the chitosan spectra is attributable to hydrogen-bonded O–H stretching vibration. According to Yu et al. (1999), the maxima for alkenes (-C=Cstretching) is 1680cm -1 , nitro compounds (NO asymmetric stretching) are 1520cm -1 , and C-O stretching is 1090cm -1 and 809cm -1 , respectively. J. Bio. & Env. Sci. 20 2 3 78 | Bhuvaneswari et al. Fig. 1. FTIR spectra of synthesized chitosan nanoparticle. To find the presence of a potential functional group for the synthesis of chitosan nanoparticles, FTIR analysis is performed. The stabilization and reduction of chitosan nanoparticles produced by green manufacturing are caused by these functional groups (Fig. 2). The hydrogen-bonded O-H stretching vibration is responsible for the prominent and broad peak in the 3500–3300 range in the chitosan spectra. Peaks for alkenes (-C=C stretching) are 1680cm -1 , nitro compounds (N-O asymmetric stretching) are 1520cm -1 , and C-O stretching is 1090cm -1 and 809cm - 1 , respectively (Yu et al., 1999). Fig. 2. FTIR spectra of chitosan-fruit peel nanocomposite. Peaks of 1680cm -1 and 1520cm -1 shifted to 1764cm -1 and 1605cm -1 , 1297cm -1 and 1181cm -1 peaks originating from nanocomposite; these shifting are due to plant extract being encapsulated in chitosan nanoparticles (Vijaya et al., 2008). Thermo Gravimetric Analysis (TGA) TGA analysis is typically used to assess sample stability and weight loss throughout a range of temperatures. The TGA analysis of the chitosan-fruit nanocomposite in the current investigation revealed degradation patterns in four stages (Fig. 3). The release of water molecules caused a weight loss of 1.82mg in the first stage, which had a total mass of 13.51mg. Chitosan breakdown caused a weight loss (6.07mg) in the second stage, which was seen at 320.3°C. Decomposition-related weight loss (9.48mg) was seen in the third stage at 508 0 C. However, the two stages of weight loss caused by the chitosan's disintegration between 320 and 508 degrees Celsius were also investigated. Mostafa et al. (2012) Chitosan nanoparticle decomposition by TG analysis was published by (Parida et al., 2013), and the report mentions two stages of decomposition at 365 o C and 500 o C. Fig. 3. Thermal degradation chitosan fruit peel nanocomposite. X-Ray Diffraction analysis (XRD) Both chitosan and chitosan fruit peel nanocomposite have been investigated in the 2 range of 10 -60 in the XRD examination. In the diffractogram of chitosan 2 values at 18.55°, 20.95°, 26.07°, and 31.88°, there is one strong peak, which is linked to the allomorphic tendency on the form of chitosan. The peaks are sharper, indicating the presence of crystal structure, as seen in Fig. 4. The ability for metal sorption may be constrained by the chitosan polymer's crystallinity. J. Bio. & Env. Sci. 20 2 3 79 | Bhuvaneswari et al. The crystallinity sizes of the chitosan nanoparticles are 2 values of 38.68, 13.52, 17.02, and 39.22nm. Fig. 4. XRD patterns of chitosan nanoparticle. Fig. 5. XRD patterns of chitosan fruit peel nanocomposite. The XRD pattern of the chitosan fruit peel nanocomposite is depicted in Fig. 5; multiple intensity peaks are seen at 2 values of 38.44 o , 44.63 o , 65.03 o , 72.55 o , and 78.14 o , which correspond to crystallinity sizes of 66.56nm, 117.74nm, 34.25nm, 18.59nm, and 21. The crystallinity of the chitosan fruit peel nanocomposite (117.74nm) increases with the degree of deacetylation and is attributed to an expansion in intermolecular hydrogen bonding due to the presence of more free NH 2 groups (Higher Degree of Deacetylation) within the molecular structure, which leads to improved packing of the macromolecular polymeric chains and an increase in crystallinity (Parida et al., 2013). Field Emission Scanning Electron Microscope On a nanoscale bar, the surface morphology of the chitosan fruit peel nanocomposite and nanoparticles was identified using a field emission scanning electron microscope (FESEM). The Chitosan nanoparticle's form and dispersion were seen in the FESEM image in Fig. 6 Fig. 6. FESEM image of poly-dispersed shaped chitosan nanoparticle. The size of the chitosan nanoparticles ranges from 75 to 130nm, demonstrating that the particles are mainly poly-dispersed in shape and some combine into bigger particles with no clearly defined morphology. By employing macerated clove buds solution, researchers have observed similar irregular shapes of chitosan nanoparticles with diameters ranging from 5 to 100nm (Vanaja et al., 2014; Sivakavinesan et al., 2014). Chitosan fruit peel nanocomposite (Fig. 7) was found to have a poly-dispersed structure, with sizes ranging from 90 to 125nm. Fig. 7. FESEM image of poly-dispersed shaped chitosan fruit peel nanocomposite. J. Bio. & Env. Sci. 20 2 3 80 | Bhuvaneswari et al. Photocatalytic degradation According to calculations, the chitosan fruit peel nanocomposite's degradation efficiency was 36.3%, 34.9%, and 36.9% at 270 minutes for various adsorbent concentrations, as shown in Fig. 8-9 shows the percentages of 57.4, 42.4, and 32.1% at 270 minutes for different dye dosages, while Fig. 10 shows the percentages of 43.4%, 31.4%, and 38.1% at 270 minutes for various dye degradation pHs. Adsorption peak at 381nm in the visible range that changed during the reaction before disappearing altogether, indicating dye degradation (Slokar and Le Marechal 1998; Tanaka et al., 2000). Fig. 8. Bar graph shows the degradation percentage of dye at different concentration. Fig. 9. Bar graph shows the degradation percentage of dye at different dosage. Fig. 10. Bar graph shows the degradation percentage of dye at different pH. Photocatalytic reaction Experiments The 1.5 L PyrexUV reactor used for the irradiation studies was wrapped in aluminum foil to improve reflection and fitted with a diving Philips HPK 125W high-pressure Tungsten lamp, which emits the most radiation at 365nm and also significantly at 435, 313, 253, and 404nm. In order to mimic the wavelengths of solar light reaching the earth's surface, a watercooled Pyrex filter blocking the transmission of wavelengths below 290nm was hooked onto the lamp. The temperature was kept at 30-35 o C using the tap water cooling circuit. Before and during the illumination, the dye solutions of 250ml volume (50mg L -1 , unless otherwise stated) were magnetically mixed with the appropriate amount of Chitosan fruit peel nanocomposite. With the exception of the tests looking at the impact of the initial pH, the solutions' pH, which varied to varying degrees, was not altered. Air was removed from the solution using an air pump and a flask containing a NaOH solution as a stopper in order to study the effects of aeration (Soutsas et al., 2010; Sami et al., 2017). The reactor was filled with solutions containing the necessary amount of dye and Chitosan fruit peel nanocomposite, and the suspensions were agitated magnetically. The light was turned on to start the photocatalytic reaction after 30 min of premixing in the dark to get the maximal adsorption of the dye onto the semiconductor surface. Chitosan fruit peel nanocomposite particles were removed from samples of 10ml by filtering them using a 0.45m Milli pore syringe filter at regular intervals. Effect of initial dye concentration It has been studied how different initial dye concentrations, ranging from 0.01 to 0.03mg L -1 at natural pH and Chitosan fruit peel nanocomposite loading of 1 g L -1 for Chitosan fruit peel nanocomposite, affect photocatalytic decolorization. As can be seen in Fig. 11, it was discovered that as dye concentration increases, the rate constant drops up to a point where zero-order reaction kinetics take over. According to Firmino et al. (2010), increasing the dye concentration from 0.01 to 0.03mg L 1 reduces the decolorization rate constant for Chitosan fruit peel nanocomposite from 80 to 300 min 1 and from 2 to 18mg/g from 30 to 80 min 1 correspondingly. J. Bio. & Env. Sci. 20 2 3 81 | Bhuvaneswari et al. Fig. 11. Effect of Adsorbent Dosages. Fig. 12. Maximum amount of dye degradation of Model dye at different adsorbent dosages with time. J. Bio. & Env. Sci. 20 2 3 82 | Bhuvaneswari et al. Using a photo reactor, the impact of chitosan fruit peel nanocomposite loading on the degradation of a model dye was examined while maintaining a constant value for all other parameters. As illustrated in Fig. 12, the apparent rate constant for the chitosan fruit peel nanocomposite at various concentrations is computed from the initial concentration and plotted against time. It is obvious that the constant rates rise with the concentration of chitosan fruit peel nanocomposite and peak at 0.05, 1.0, and 1.5 g/L L 1 chitosan fruit peel nanocomposite. The point at which the entire catalytic surface is fully lit varies on a number of variables, including the geometry and operating conditions of the reactor, the wavelength, and the intensity of the light source (Hameed and ElKhaiary, 2008a; Hameed et al., 2008b). The ideal catalyst loading is discovered to be reliant on the starting solute concentration because as the adsorbent dosage is increased; the total active surface area increases, making more active sites on the catalyst surface available. Particle aggregation may also lessen the adsorbent dosage activity at high concentrations by decreasing the specific surface, Effect of solution pH Solution pH is the primary factor that affects photocatalytic degradation. Using an initial concentration of 0.02mg L 1 , a light intensity of 2.5 mWcm 2 , and a chitosan fruit peel nanocomposite loading of 1 g L 1 for adsorbent doses, the effect of pH on the photocatalytic degradation of Model dye was investigated. In alkaline solutions, the pH was modified using NaOH, whereas in acidic solutions, it was altered using H 2 SO 4 (Namasivayam and Kadirvelu, 1994; Namasivayam, 1995). Fig. 13 illustrates how changing the starting pH of an aqueous solution between 4.0 and 9.0 affects the apparent rate constant of photocatalytic degradation. Near the TiO 2 point of zero charges (pHpzc = 7.5), photocatalytic activity peaked, while the apparent rate constant decreased in alkaline circumstances. The results showed that the degradation apparent rate constant for chitosan fruit peel nanocomposite reduced with an increase in pH from 7.5 to 9.0, increased until the optimum (pH7.5), and subsequently declined in an alkaline medium. The model color of degradation for chitosan fruit peel nanocomposite rises with an increase in pH from 7.5 to 9.0 (natural pH), and then falls in alkaline medium. It is clear from Fig.13 that the initial pH has a significant impact on the adsorption state, which is necessary to achieve maximum dye removal. The association between dark adsorption and photocatalytic degradation was not seen in natural media, though. The molecular form of Model dye is typical at pH values less than 4.0, and the ionic form is typical at pH values higher than 7.5. The structure of the Model dye is in line with pH values. Both kinds of Model dye can be found at pH levels between 4.0 and 7.5. Since the chitosan fruit peel nanocomposite has a pH of around 7.5, its surface is positively charged in an acidic environment (pH 7.5) and negatively charged in an alkaline environment. The coupling of Model dye molecules with chitosan fruit peel nanocomposite particles is favored in acidic to neutral media due to the effect of charges attraction between negatively charged Model dye molecules and positively charged chitosan fruit peel nanocomposite particles. Fig. 13. Maximum amount of dye degradation of Model dye at different pH with time. Due to the creation of an H-bond between the proton from the catalyst and the lone pair of electrons on the SO 3 group of the dye, the dye is firmly adsorbed on the photocatalyst in acidic solutions, which causes a significant degree of decolorization (Ong et al., 2010; J. Bio. & Env. Sci. 20 2 3 83 | Bhuvaneswari et al. Ozdes et al., 2010). Repulsive forces between negatively charged Model dye molecules (SO 3 - ions) and negatively charged chitosan fruit peel nanocomposite particles reduced the dye's adsorption at alkaline pH, where •OH was anticipated to be the dominant species. Wastewater treatment-Photo catalytic degradation In the process of treating wastewater, the pollutant concentration is a crucial factor. Real textile effluent was used in the studies to test the efficiency of semiconductor photocatalytic treatment. The wastewater's maximum absorbance wavelength, max = 550nm, was used to measure the wastewater's decolorization. Before beginning the biological treatment, the textile effluent was obtained and used directly, undiluted (Mary-Helen et al., 2012; Min et al., 2012). Table 1. Characteristic of physical and chemical parameters for Industry wastewater. Site Site - 1 (Noyyal river) Site-2 (Rayapuram) Site-3 (Anaipalayam) pH at 37 o C 10.1±0.1 11.1±0.1 14.5±0.1 TDSmg / l 530 623 299 TSSmg / l 93 95 118 BOD 5mg /l 320 280 240 CODmg / l 512 448 416 Fig. 14. Maximum amount of dye degradation of Industry wastewater at different Adsorbent dosages with time (NOYYAL River). The sewage was examined. Table 1. Shows physical and chemical properties were investigated. The decolorization results for a 300-minute treatment are shown in Figs. 14, 15, and 16 for the dye concentration at Noyyal River, Rayapuram River, Anaipalayam industry effluent water and Industry dye at the Site with constant composite concentration. Fig. 15. Maximum amount of dye degradation of Industry wastewater at different Adsorbent dosages with time (RAYAPURAM - River). Fig. 16. Maximum amount of dye degradation of Industry wastewater at different Adsorbent dosages with time (ANAIPALAYAM - RIVER). Complete decolorization of the wastewater was achieved within 300 min h, but the detoxification of the wastewater was only partly achieved (≈35% for 300 min treatment). It is obvious that prolonged irradiation is needed, in order to achieve total destruction of the contaminants, thus, resulting in the high cost of the method. However, when facing the problem of pollution the combination of methods could be the key to the total solution. Photocatalytic treatment in general has higher operating costs than those of a biological treatment.