Fe3O4-Poly(1,2-Bis(methacryloxy)ethane-co-4-vinylbenzylchloride)-TiO2 Magnetic Hybrid Composite Particles for the Treatment of Colored Organic Pollutants

Abstract

The invention relates to Fe3O4-poly(1,2-Bis(methacryloxyoxy)ethane-co-4-vinylbenzylchloride)-TiO2 magnetic hybrid adsorbent-photocatalyst composite particles developed for the treatment of colored organic pollutants and residues from wastewater of various industrial facilities in the chemical industry, environmental technologies, textile industry, and similar sectors. The invention specifically concerns magnetic hybrid adsorbent-photocatalyst composite particles [Man-poly(BME-co-VBK)-photo] and their synthesis, for the efficient removal of azo and aromatic dyes, pharmaceutical residues, and other organic pollutants from aqueous solutions through simultaneous adsorption and photocatalytic decolorization.

Description

1 TARIFF Fe₃O₄-Poly(1,2-Bis(methacryloxyoxy)ethane-co- for the Treatment of Colored Organic Pollutants 4-vinylbenzylchloride)-TiO₂ Magnetic Hybrid Composite Particles Technical Area The invention has applications in various industries such as the chemical sector, environmental technologies, textile industry, and similar fields. for the treatment of colored organic pollutants and residues from wastewater of facilities enhanced Fe3O4-poly(1,2-Bis(methacryloxy)ethane-co-4-vinylbenzylchloride)-TiO2 magnetic This relates to hybrid adsorbent-photocatalyst composite particles. The invention deals with, in particular, azo and aromatic dyes, pharmaceutical residues and other organic pollutants. Simultaneously via adsorption and photocatalytic decolorization from aqueous solutions 10 Magnetic hybrid adsorbent-photocatalyst composite for effective removal. It is concerned with the particles [Man-poly(BME-co-VBK)-photo] and its synthesis. State of the Art Wastewater contains organic matter, particularly from industrial sectors such as textiles, chemicals, and pharmaceuticals. Due to pollutants and paint residues, this poses a significant environmental risk. pollutants cause problems such as color, toxicity, and biodegradability in water sources. It opens up and creates negative impacts on the ecosystem and human health. Industrial Large-scale wastewater treatment ensures both compliance with environmental standards and sustainable water management. It is of critical importance in this respect. 20 Traditional methods used for wastewater treatment are physical (sedimentation, filtration), chemical (coagulation, ozonation, adsorption, ion exchange) and biological (biological oxidation with microorganisms) are techniques (Saravanan et al., 2021; Surela et al., (2024). These methods are insufficient for low concentrations of pollutants, and in some cases, side effects occur. They are able to create products and are unable to completely remove persistent organic components. Specifically... Complex organic pollutants such as azo and aromatic dyes are effectively removed by conventional methods. It cannot be removed in this way. Photocatalytic oxidation, one of the advanced oxidation methods, allows semiconductors to be oxidized under light for 30 minutes. It relies on the production of radicals by forming electron-hole pairs, along with adsorption. When used, it provides higher efficiency in the removal of organic pollutants. 2 (Miklos et al., 2018; Saravanan et al., 2022). However, TiO₂-based photocatalysts It is only active under UV light and, due to its wide bandwidth (~3.2 eV), is suitable for industrial scale. It has disadvantages such as high energy cost and limited visible light efficiency (Samuel (et al., 2022). In addition, the photocatalytic efficiency of fast recombination of electron-hole pairs. It restricts (Moss et al., 2017). 5 TiO₂-supported treatment for the removal of organic pollutants and pharmaceutical residues from wastewater. Photocatalysis studies are common. TiO₂ composites combined with Fe₃O₄ are used in photocatalysis. It combines its advantage with the ease of magnetic recovery (Jacinto et al., 2020). With Fe₃O₄ If combined TiO₂ composites combine the advantage of photocatalysis with magnetic recovery, 10 However, in existing multilayer systems (e.g., Fe₃O₄@SiO₂@TiO₂), the photocatalyst surface is the same. It also functions as an adsorbent. This means that pollutants adhere excessively to the surface. It restricts light access as a result of adsorption or attachment of by-components, and radicals It reduces photocatalytic efficiency by limiting the production process from reaching the target pollutants. (Allam et al., 2024; Çimen et al., 2024). 15 Similar problems have been observed in polymer-supported hybrid TiO₂ systems. For example, Monomer aromatic structure in vinylphosphonic acid (VPA) based polymer–TiO₂ spheres The absence of these features limits its capacity for π–π interactions, particularly with azo and aromatic dyes. Therefore, it restricts selective adsorption (Özel Ş., 2018). Also, the polymer matrix 20 Partial coating of the TiO₂ surface reduces photocatalytic efficiency by preventing light penetration. And because the recombination rate of electron-hole pairs is high, the decay rate It reduces (Miklos et al., 2018; Moss et al., 2017). The following applications were encountered in the literature review: 25 Patent application number CN1562464A describes a type of magnetic device that utilizes magnetic recovery. This relates to nano TiO2 composite photocatalysts and their preparation method. Here, Fe₃O₄ a multilayer magnetic photocatalyst consisting of a core, a SiO₂ interlayer, and a TiO₂ shell It has been defined. However, the polymer matrix is ​​not present on a substrate and the surface is functional. Selective adsorption is not possible because there are no groups. Furthermore, the system cannot be exposed to UV or 30°C. Detailed information regarding its photocatalytic activity under visible light is not provided. Patent application number US11972886B2 involves embedding non-magnetic microparticles. This relates to hybrid nanoparticles. Here, a particle is defined as containing at least one polymeric material. numerous magnetic inorganic or organic particles embedded within microparticles However, the photocatalytic function of the system, TiO₂ doping, and light transmittance are considered. 35 3 No data has been obtained on the radical formation mechanism and photocatalytic performance. It is not available. Patent application number TR2019 / 15938 concerns wastewater in the textile industry. organic ion exchange resins in chromatographic applications in systems Cross-linked 5 developed for use in the decolorization-degradation of dyes. This relates to a bonded, porous polymer composite material and its production method. Magnetic poly(EGDMA-vinylphosphonic acid) composite particles have been developed, and photocatalysis and Adsorption processes have been considered as separate mechanisms. Polymer architecture, light reducing transmittance, photocatalyst placement, and electron-hole recombination. Detailed solutions have not been offered for this. 10 These situations necessitate both adsorption and photocatalysis in current hybrid photocatalyst systems. optimizing the activity and achieving high efficiency across a broad spectrum of pollutants This shows that it is limited. Therefore, in the current state of the technique, the polymer matrix It possesses light transmittance that effectively integrates a magnetic core and a TiO₂ photocatalyst. And a new hybrid system is needed that radically optimizes its production. 15 In conclusion, due to the negative aspects described above and the current solutions, the subject matter... Due to its shortcomings, an improvement is needed in the relevant technical field. It has been made. The purpose of the invention The present invention meets the aforementioned requirements while eliminating all disadvantages. A polymer matrix magnetic hybrid adsorbent that removes and offers some additional advantages. It deals with photocatalyst composite particles and their synthesis methods. 25 The primary purpose of the invention is to remove colored organic pollutants and residues from industrial wastewater. with high efficiency, simultaneously through adsorption and photocatalytic decolorization. The aim is to eliminate it. The aim of the invention is to magnetically attach composite particles using an Fe₃O₄ magnetic core. to impart properties that allow for easy separation with the help of a magnet after the reaction. The goal is to ensure reusability. One aim of the invention is to create a porous 35 poly(4-vinylbenzylchloride-co-1,2-Bis(methacryloxy)ethane) By efficiently integrating the polymer matrix and TiO₂ photocatalyst, the system's light... 4 Optimizing permeability and radical production, of pollutants and radical species By facilitating diffusion through pores, it enhances adsorption and photocatalysis processes. The goal is to make them simultaneous and effective. Another objective of the invention is to produce azo and aromatic 5-valent compounds thanks to the aromatic ring of vinylbenzyl chloride. By interacting π–π with dyes, pollutants concentrate on the surface and are selective. The goal is to increase adsorption. Another objective of the invention is to immobilize surface-fixed TiO₂ nanoparticles and –CH₂Cl groups. Photocatalytic degradation by reducing electron-hole pair recombination through inductive effect 10 The goal is to increase its speed. Another aim of the invention is to enable the reaction of composite particles thanks to a magnetic core. The goal is to ensure that it can be easily separated and reused afterwards. Another aim of the invention is to target different types of pollutants (azo and aromatic dyes, pharmaceuticals) The goal is to develop a highly applicable, broad-spectrum treatment system for (residues, etc.). Another aim of the invention is to create a system that efficiently combines adsorption and photocatalysis. A new generation of magnetically separable and functionally improved materials 20 to present. To achieve the purposes described above, the invention enables the treatment of wastewater from industrial facilities. Simultaneous adsorption and photocatalytic effects on colored organic pollutants and residues. Polymer matrix magnetic 25 for use in decolorization processes They are hybrid adsorbent-photocatalyst composite particles, using benzoyl peroxide as an initiator. pure water for the dispersion phase and polyvinyl alcohol as a stabilizer, 4- as a monomer. vinylbenzyl chloride, 1,2-Bis(methacryloxy)ethane as crosslinker, magnetic core. It contains Fe₃O₄ nanoparticles as a photocatalyst and TiO₂ nanoparticles as a photocatalyst. It is. 30 To achieve the purposes described above, the invention enables the treatment of wastewater from industrial facilities. Simultaneous adsorption and photocatalytic effects on colored organic pollutants and residues. Polymer matrix magnetic for use in decolorization processes. This is a synthesis method for hybrid adsorbent-photocatalyst composite particles, and the following 35 It includes the following steps; a. Distribution phase by stirring polyvinyl alcohol until it dissolves in pure water. preparation, b. Mixing 4-vinylbenzyl chloride and 1,2-Bis(methacryloxyyl)ethane to form the organic phase. preparation, c. Adding TiO₂ and Fe₃O₄ nanoparticles to the dispersion phase and mixing, 5 d. Distribution of the phase with added nanoparticles in the sonicator, e. Addition of the organic phase to the dispersion phase f. Reacting the mixture by suspension polymerization, g. Washing and decanting of composite particles formed after the reaction. h. Drying the prepared particles and sieving the dried particles 10 The structural and characteristic features and all the advantages of the invention are given in the figures below. Thanks to the detailed explanation written with references to the figures, it becomes clearer. This will be understood. Therefore, the evaluation should also take these figures and detailed explanations into account. It must be done by taking 15. Ways to Help Understand the Discovery Figure 1. XRD diffraction graph: Synthesized Fe₃O₄–poly(1,2-bis(methacryloxy)ethane-co- Diffraction patterns and phase couplings of vinylbenzyl chloride (V1)–TiO₂ composite particles. (Anatase TiO₂, Rutile TiO₂, Magnetite Fe₃O₄). 20 Figure 2. FT-IR spectrum: Synthesized Fe₃O₄–poly(1,2-bis(methacryloxy)ethane-co- functional groups in vinylbenzyl chloride (TiO₂) composite particles Figure 3. SEM image: synthesized Fe₃O₄–poly(1,2-bis(methacryloxy)ethane-co-vinylbenzyl Surface morphology and porous structure of (chloride)–TiO₂ composite particles. Figure 4. EDS spectrum: Synthesized Fe₃O₄–poly(1,2-bis(methacryloxy)ethane-co-vinylbenzyl 25 Fe, Ti, and O distributions in (chloride)–TiO₂ composite particles Figure 5. EDS elemental analysis map: synthesized Fe₃O₄–poly(1,2- Fe, Ti and O in bis(methacryloiloxy)ethane-co-vinylbenzyl chloride)–TiO₂ composite particles. distributions Figure 6. Removal of AR114 by its adsorbent under daylight. 30 Figure 7. Linear regression of acid red 114 removal by adsorbent under daylight. Figure 8. Variation of adsorption capacity of adsorbent with pH. Figure 9. Variation of adsorption capacity of adsorbent with adsorbent amount. Figure 10. Variation of adsorption capacity of adsorbent with temperature and time. Figure 11. Adsorption–Desorption Isotherm of the Adsorbent N₂ 35 6 Figure 12. Graph of pore size distribution of hybrid adsorbent determined according to BJH method. Figure 13. Post-adsorption FT-IR graph of adsorption of adsorbent on AR114. Detailed Description of Find This detailed explanation of the invention only provides 5 points to help better understand the subject. and is explained in a way that will not create any limiting effects. The invention describes a polymer matrix containing a functional group and which is magnetically separable. Magnetic hybrid adsorbent-photocatalyst composite particles have been developed. These particles... In its preparation; 4-10 functional groups containing Fe₃O₄ around a magnetic core vinylbenzyl chloride monomer and 1,2-Bis(methacryloxy)ethane as crosslinking agent. Suspension polymerization method was applied using this method. The resulting poly(4- vinylbenzylchloride-co-1,2-Bis(methacryloxy)ethane) porous polymer spheres, on the surface It is supported by fixed TiO₂ nanoparticles. The invention concerns the purification of wastewater from industrial facilities from colored organic pollutants and residues. in the treatment through timed adsorption and photocatalytic decolorization processes Magnetic hybrid adsorbent-photocatalyst composite with polymer matrix for use particles; benzoyl peroxide as initiator, pure water for dispersion phase and as stabilizer. Polyvinyl alcohol, 4-vinylbenzyl chloride as monomer, 1,2-20 as crosslinking agent. Bis(methacryloxy)ethane, Fe₃O₄ nanoparticles as magnetic core and photocatalyst. It contains TiO₂ nanoparticles. Table 1 Preferred and usable quantities by weight of the composite particles subject to the invention. Preferred by Weight amount (%) Available by Weight amount (%) Pure water 80.873 75-84 Polyvinyl alcohol 0.323 0.2-0.5 1,2- Bis(metaacryloxy)ethane 9,618 8-12 4-vinylbenzylchloride 7,406 6-10 Benzoyl peroxide 0.162 0.1 - 0.3 Fe3O4 0.809 0.5-1.5 TiO2 0.809 0.5 -1.5 7 The subject of the invention is magnetic hybrid adsorbent-photocatalyst composite particles; 0.1% by weight - 0.3% benzoyl peroxide, 75-84% pure water, 0.2-0.5% polyvinyl alcohol, 4-vinylbenzyl chloride in the range of 6-10%, 1,2-Bis(methacryloxy)ethane in the range of 8-12%, It contains 0.5-1.5% Fe₃O₄ and 0.5-1.5% TiO₂. The subject of the invention is magnetic hybrid adsorbent-photocatalyst composite particles, the characteristic of which is; 0.162% benzoyl peroxide by weight, 80.873% pure water, 0.323% polyvinyl alcohol, 7.406% 4- vinylbenzylchloride, 9.618% 1,2-Bis(methacryloyloxy)ethane, 0.809% Fe₃O₄ and 0.809% TiO₂ It includes. Fe₃O₄ core: Imparts magnetic properties to composite particles, thus facilitating the reaction. Afterwards, it can be easily separated from the solution with the help of a simple magnet. This magnetic property, It increases reusability and provides ease of use in industrial applications. Porous poly(4-vinylbenzylchloride-co-1,2-Bis(methacryloxyyl)ethane) polymer matrix: 15 It allows pollutants and radical species to diffuse through the pores, thus Adsorption and photocatalysis occur simultaneously and efficiently. (vinylbenzyl chloride) Thanks to its aromatic ring, it interacts π–π with azo and aromatic dyes; in this way Pollutants concentrate on the polymer surface, and selective adsorption is achieved. Surface-fixed TiO₂ nanoparticles: Nanoparticles are directly exposed to light. Thus, the light shadowing problem is eliminated. – Inductive effect of CH₂Cl groups, It reduces the recombination of electron-hole pairs and increases radical production. As a result... The rate of photocatalytic degradation increases. The invention combines adsorption and photocatalysis efficiently using magnetic technology. It offers a new generation of material that is detachable and functionally upgradeable. The system, highly efficient removal of colored organic pollutants and residues from industrial wastewater. It enables the elimination of the problem. The invention involves the synthesis of polymer matrix magnetic hybrid adsorbent-photocatalyst composite particles. This relates to the method and includes the following steps: a. Distribution phase by stirring polyvinyl alcohol until it dissolves in pure water. preparation, b. Mixing 4-vinylbenzyl chloride and 1,2-Bis(methacryloxyyl)ethane to form an organic phase of 35 preparation, 8 c. Adding TiO₂ and Fe₃O₄ nanoparticles to the dispersion phase and mixing them, d. Distribution of the phase with added nanoparticles in the sonicator, e. Addition of the organic phase to the dispersion phase f. Reacting the mixture by suspension polymerization, g. Washing and decanting of the composite particles formed after the reaction 5 h. Drying the prepared particles and sieving the dried particles. The invention describes a method consisting of: a. in the process step, polyvinyl alcohol and pure water preferably heated with a magnetic field. The dispersion phase is prepared by mixing in a mixer at a speed of 400–1000 rpm. 10 In the b. process step of the method that is the subject of the invention, 4-vinylbenzyl chloride and 1,2- Bis(methacryloxy)ethane is preferably stirred in a heated magnetic stirrer at a speed of 400–1000 rpm. The organic phase is prepared by mixing. The invention describes a method involving the following: c. Addition of TiO₂ and Fe₃O₄ nanoparticles to the dispersion phase in process step. It is preferably added by mixing in a heated magnetic stirrer at a speed of 400–1000 rpm. In the method described in the invention, the phase to which nanoparticles are added is preferably Bandelin RK 255 H. 20 in an ultrasonic bath at 35 kHz frequency and 160 W HF output power for 2 minutes. It is subjected to sonication. (step d) The invention describes a method in one of its applications; a drip funnel connected to an organic phase reactor. With the help of, it is added to the dispersion phase in a controlled manner at a flow rate of approximately 5 mL / min. is being done. (step e) 25 The invention describes a method where suspension polymerization in step f is preferably performed at 55–65 °C. The process is carried out for 4-24 hours at temperatures within this range, and for 6 hours at 60°C. In one application of the method described in the invention, the synthesized composite particles are reacted in 30 seconds. Finally, it is washed three times with room temperature distilled water. 10 in each washing cycle. The system is shaken for a minute and then allowed to collapse on its own for 10 minutes. After a few minutes, the liquid phase separates from the system through natural decantation (step g). The invention concerns a method where, in step h, the particles prepared are preferably heated at 40–130 °C 35 It is dried at a temperature within this range for 8–24 hours. 9 The method described in the invention involves drying particles, preferably 45–500 µm, in step h of the process. It is fractionated by sieving through sieves within a certain range. In this method, the sieving process is preferably done with a mechanical sieve. The invention describes a method involving the preparation of the dispersion phase, the organic phase, and magnetic... Heated magnetic stirrer for homogeneous addition of photocatalytic particles to the system. It is used. Ensuring a homogeneous mixture is important for the efficiency of polymerization. It is important. The invention describes a method that ensures homogeneous distribution and a stable droplet structure. A sonicator is used to facilitate the formation of this spherical polymer. This step (step d) It is crucial in terms of particle size control and porosity. The dispersion phase disperses in the organic phase and this suspension polymerization is controlled. 15 To ensure these processes are carried out under the specified conditions, they are performed inside the reactor. In addition, particles are also used in washing and decantation processes after reactor polymerization. It is used in purification. The particles obtained after polymerization are dried in an oven, and thus... Drying is achieved at a controlled temperature. This stabilizes the particles and 20 It is prepared for characterization / application studies. Homogeneous fractions are obtained by sifting the dried particles according to their size distribution. This ensures that particle size affects adsorption and photocatalytic performance. It is important for controlling its effect. 25 The parameters that can be used for the method described in the invention are given in Table 2. Table 2 Parameters | Preferred target | Applicable range | Relevant steps Reaction temperature (polymerization) 60 °C 55–65 °C ef steps Mixing speed 700 rpm 400–1000 rpm increments Polymerization time: 6 hours, 4–24 hours, step f. Drying temperature 60 °C, 40–130 °C per hour. Drying time 12–16 hours 8–24 hours h step Sieving (sieve range) 50–312 µm 45–500 µm h step An application of the method described in the invention is given below; a) Preparation of the dispersion phase: Polyvinyl alcohol is placed in a beaker, pure water is added, and magnetic solution is obtained. Mix in a mixer at 60°C and 400 rpm until completely dissolved. 5 It is mixed. b) Preparation of the organic phase: 1,2-Bis(methacryloxy)ethane was placed in a separate beaker and 4- Vinylbenzyl chloride monomer is added and stirred on a magnetic stirrer. c). Addition of magnetic / photocatalytic fillers: Mixing dispersion in the magnetic stirrer. TiO2 and Fe3O4 were added to the phase. 10 d) Dispersion of the dispersion phase in the sonicator: The mixture prepared in the previous step is dispersed in the sonicator. It has been distributed. e) Phase combination: The dispersion phase is introduced into the reactor, and the organic phase is gradually added. It has been added. f) Suspension polymerization: Once the phases have combined, the reaction is carried out at 60 °C ± 2 15 The process was maintained for 6 hours in a reactor set at °C and 700 rpm. g). Washing and decantation: At the end of the reaction, the reactor is closed and the mixing chamber is closed. It was cooled to its temperature. Then the solid product was washed. h) Drying: The resulting product was dried in an oven / vacuum oven at 60 °C for 12–16 hours. The dried particles were then sieved using sieves of appropriate size. 20 Experimental Analysis and Results 1. X-ray diffractometer (XRD) diffraction pattern graph: X-ray diffraction allows the phases contained within a material to be determined by examining its crystal structure. Quantitative / qualitative phase analysis can be performed, and crystal sizes and lattice constants can be calculated. This crystal structures of magnetic-photocatalytic composite particles synthesized in the study A PANalytical EMPYREAN X-ray diffractometer was used in the examination. In the analyses Cu-Kα radiation (λ = 1.54046 Å) was preferred, and measurements were taken at 45 kV voltage and 40 mA current. Measurements were taken at 25°C. Scans were conducted between 5–90 11 in the range of (2θ), and with the scanning speed fixed at 2° / min in continuous scanning mode It has been done. (Figure 1) The diffraction patterns obtained from the analysis were processed using ICDD / JCPDS data standard cards. Compared. The characteristic peaks observed in the obtained diffraction pattern are; 25.3° (101), 37.9° (004), 48.1° (200), 54.0° (105), 55.1° (211), 62.7° (204), 68.8° (116), 70.3–70.8° (220), 5 With values ​​of 75.0–76.0° (215) and 82.9–83.3° (312), this pattern is JCPDS No. 21-1272 It was found to be compatible with the anatase TiO₂ phase. It belongs to the rutile TiO₂ (JCPDS No. 21-1276) phase. Characteristic peaks are 27.4° (110), 36.1° (101), 41.2° (111), 54.3° (211), 56.6° (220) and 69.0° (301) values ​​are observed. However, the corresponding diffraction pattern obtained Weak signals were detected in these regions. This indicates that the rutile phase is present in very low amounts. This indicates the presence of the characteristic magnetite (Fe₃O₄) (JCPDS No. 19-0629) phase. peaks at 30.1° (220), 35.5° (311), 43.1° (400), 53.4° (422), 57.0° (511) and 62.6° (440) It has been observed that they are compatible. Accordingly, the obtained peaks are; anatase TiO₂ (JCPDS No. 21- It was found to be compatible with magnetite Fe₃O₄ (JCPDS No. 19-0629) phases (1272). 2. Fourier Transform (FT-IR) spectrum: FT-IR spectra were obtained using an ATR apparatus on the Bruker FTIR device at a depth of 0.2 cm-1. It was recorded at a resolution of 2920–2850 cm⁻¹ (Figure 2). Observed in the FTIR spectrum at 2920–2850 cm⁻¹ The bands are based on a polymer backbone of 1,2-bis(methacryloxy)ethane-co-vinylbenzyl chloride. The aliphatic C–H stretching corresponds to a strong signal around 1720–1730 cm⁻¹, indicating that the polymer is C=O 20 This corresponds to the stress. C–O–C vibrations are prominent in the range of 1250–1140 cm⁻¹. As seen in the figure, the aromatic ring of vinylbenzyl chloride is located in the 1600–1500 cm⁻¹ region. C=C vibrations and –CH₂ bending around 1440–1460 cm⁻¹ are observed. 3400–3200 The band surface shows –OH groups, seen as a broad shoulder between cm⁻¹, 1050–1000 Ti–O–C / C–O–Ti signals in the cm⁻¹ region indicate polymer–TiO₂ interface interactions. It shows aromatic C–H external plane vibrations at 830–700 cm⁻¹, and at 669 and 632 cm⁻¹. These are characteristic vibrations of inorganic phases, in the 590–630 cm⁻¹ band of Fe–O (magnetite). with its vibrations, the 640–660 cm⁻¹ band is compatible with Ti–O–Ti (anatase TiO₂) vibrations. These findings indicate that the synthesized composite contains both functional groups of polymer network. and that it carries the characteristic bond vibrations of the TiO₂ and Fe₃O₄ phases and 30 This indicates that the polymerization process is complete. 12 3. SEM-EDS mapping: SEM images show synthesized Fe₃O₄–poly(1,2-bis(methacryloiloxy)ethane-co-vinylbenzyl (chloride)–TiO₂ composite particles generally have a spherical morphology. This is observed (Figure 3). Porous regions on the surface represent phases formed in the polymer matrix. micro-spaces and the distribution of inorganic components (TiO₂, Fe₃O₄) in some regions 5 This indicates that this structure has the potential to increase the effective surface area for adsorption. When the EDS semi-quantitative analysis results shown in Figure 4 are evaluated, the particle In the center, the Fe signal is high and the Ti signal is low, and as we move towards the surface, the Ti signal decreases. It has been observed that the ratio has increased. This distribution indicates that Fe₃O₄ is present in the nuclei of the particles at a rate of 10⁻¹⁰. This shows that the concentration is high, and TiO₂ is present in a fixed structure on the surface. The higher oxygen content found at the surface is also a finding consistent with the TiO₂ shell. Figure 5 shows the EDS elemental analysis map. Thus, the SEM-EDS results are presented. This shows that the synthesized composite formed in a way that was suitable for the targeted structure. This 15 Morphological and elemental distribution characteristics were obtained, supported by XRD and FT-IR results. The resulting structure will have both an Fe₃O₄ core that provides magnetic separation properties and It shows that the composite has a TiO₂ structure that will increase photocatalytic activity. It proves its suitability for adsorption-photodegradation studies. Adsorption Capacity and Photocatalytic Efficiency of Hybrid Adsorbent Determination Textile, plastics, cosmetics, food and especially industrial dyeing worldwide. More than 700,000 tons of synthetic dyes are produced annually in these processes, and approximately 60% consists of azo dyes. Azo dyes are those containing –N=N– 25 within the molecule. Characterized by the presence of the azo group, and having bright colors, high color rendering power, and Synthetic dyes are widely preferred due to their economic advantages. This class of dyes... It contains azo, anthraquinone, thiazine and xanthene type dyes. (Rajeshwar et al., 2008). Acid Red 114 (AR 114) is a water-soluble dye belonging to the class of acidic dyes. It is a soluble and anionic azo dye. AR 114, 30, has the molecular formula C₃₇H₂₈N₄Na₂O₁₀S₃. especially in the textile industry for dyeing natural fibers such as wool, silk and jute It is used (PubChem, 2024). In the presence of titanium dioxide and light, acid red 114 It has been reported to be unstable (Nikazar et al. 2018) and the model has been used as a pollutant. [Man-poly(BME-ko-VBK)-foto] hybrid adsorbent-photocatalyst system in textile wastewater High efficiency for azo dye removal by combining adsorption and photocatalysis 35 13 It offers. Indeed, adsorption and... in the removal of dyes from water The simultaneous use of photocatalysis is considered an innovative method. The combined use of adsorption and photocatalysis in the literature also highlights the importance of each process. High efficiency, broad pollutant spectrum, low operating costs thanks to the combination of its advantages. It offers advantages such as low cost and easy recycling. 5 When Figures 6 and 7 are evaluated, it can be seen that the adsorbent is also fast and effective. It appears to exhibit photocatalytic activity. In the preliminary study, it was also shown that Acid Red 114 (AR114) dye could be removed using a hybrid structure. First, the paint is taken up onto the surface by adsorption, and then under visible light for 10 minutes. It occurred in two stages in the form of photocatalytic degradation. Equilibrium studies were conducted, Hybrid particles exhibit high adsorption over a wide pH range (3–9) and especially at neutral pH. It has been shown to exhibit capacity. This pH is also its own natural pH in model pollution. This is an important point that distinguishes it from existing studies. Table 3 Isotherm data of adsorption of adsorbent on AR114. Temperature °C LANGMUIR ISOTHERM SAB TITLES KL (L / mg) Q max (mg / g) R2 RL 4 0.00664794 526.315789 0.9263 0.8771 -0.2502 0.00575687 526.315789 0.9766 0.8854 -0.2786 45 0.00344632 555.555556 0.9353 0.9207 -0.3870 65 0.00261867 476.190476 0.92 0.9363 -0.4514 Temperature °C FREUNDLICH ISOTHERM SAB ITLERI KF (mg / g)(L / mg) 1 / nn R2 4 1.6254859 1.23793018 0.9994 1.1789261 1.21639703 0.9954 45 1.7847276 1.1265067 0.9848 65 2.7140188 1.24843945 0.9963 Temperature °C Dubinin-Radushkevich 14 QD-R (mg / g) KD-R x 109 (mol2 / J2) Efe (kJ / mol) R2 4 468.633618 0.00 9.12870929 0.998 380.110519 0.00 9.12870929 0.9918 45 384.570201 0.00 9.12870929 0.999 65 371.234659 0.00 9.12870929 0.9944 The maximum measured AR114 adsorption capacity is approximately 526 mg / g at 25 °C. The value is quite high compared to many traditional adsorbents. Freundlich parameters The study showed that the system has a heterogeneous surface; KF increases with temperature, while the value of n... The fact that it remains in the 1–2 range indicates that adsorption is favorable and mostly physical in nature. It has supported the DR model, which also provides higher capacity at lower temperatures, approximately 9.5. An adsorption energy of kJ / mol indicates predominantly ion-exchange physical interactions. This has been shown. When the models are evaluated together, Freundlich's highest fit is observed. provided by; Langmuir and D-R, on the other hand, investigated the chemical and physical adsorption mechanism. It appears to support this. These results indicate that the studied adsorption process is temperature-sensitive. It shows that it has an exothermic and surface-controlled mechanism. Isotherm 10 The data should also support heterogeneity and reusability. Table 4 shows the pore size distribution of the hybrid adsorbent determined according to the BJH method. Method Surface Area (m² / g) Pore Volume (cm³ / g) Pore ​​Radius (Å) BJH Adsorption 15.08 0.055 40.7 BJH Desorption 23.68 0.063 40.7 The material exhibits Type IV isotherm and hysteresis, indicating a mesoporous structure. The ring is visible. "As a result of BJH adsorption and desorption analyses, the sample's The dominant pore radius was determined to be approximately 4 nm, which indicates a mesoporous character. This shows that the surface area calculated from adsorption and desorption data is 15–24 20 The density was found to be m² / g, and the pore volume was in the range of 0.055–0.063 cm³ / g. These results indicate that the composite... This confirms that the structure has a mesoporous composition. The peak in the aromatic region (1450–1600 cm⁻¹) in the FT-IR spectrum after adsorption. The significant increase in intensity caused the aromatic rings of the azo dye to adhere to the composite surface. This reveals that it is related. Furthermore, it appears in the spectrum in the range of 1380–1440 cm⁻¹. The newly observed peaks correspond to the characteristic N=N vibrations of azo dyes. This is a typical signal that appears after adsorption. 1000–1200 cm⁻¹ 5 belonging to sulfonate groups. The prominence of strong S=O stretching bands in the region indicates that the paint is –SO₃⁻ functional. This shows that the group is fixed on the surface. At the ester carbonyl peak of the polymer (1715– The observed increase in intensity (1730 cm⁻¹) is due to the combination of the dye's –SO₃⁻ groups and the polymer's C=O groups. It is thought that this is due to electrostatic interactions between them. The broadened -OH peak in the spectrum (3200–3600 cm⁻¹) is associated with the hydrophilic groups of the dye. It is due to hydrogen bonds between the –OH groups on the Fe₃O₄ / TiO₂ surface. It is thought that Technical advantages of the hybrid structure include its ability to capture a wider portion of the solar spectrum. Ability to utilize (visible light activity), adsorption and oxidation within a single particle 15 By combining the steps, it achieves higher efficiency and speed compared to traditional methods. This ensures easy recovery via magnetic field without the need for an external separation process. to be able to recover and maintain its chemical and mechanical stability during long-term use These advantages make our hybrid system significantly superior to existing wastewater treatment technologies. This makes it an innovative solution with significant advantages. 20 16 REFERENCES  Allam, O., Maghsoodi, M., Jang, S. S., & Snow, S. D. (2024). Unveiling competitive adsorption in TiO2 photocatalysis through machine-learning-accelerated molecular dynamics, DFT, and experimental methods. ACS Applied Materials & Interfaces, 16(28), 5 36215–36223. doi:10.1021 / acsami.4c02334  Cimen, A., Bilgic, A., & Bayrak, M. (2024). Fabrication and characterization of new Fe3O4@SiO2@TiO2-CPTS-HBAP (FST-CH) nanoparticles for photocatalytic degradation and adsorption removal of rhodamine B dye in the aquatic environment. Heliyon, 10(7), e29355. doi:10.1016 / j.heliyon.2024.e29355 10  Jacinto, M. J., Ferreira, L. F., & Silva, V. C. (2020). Magnetic materials for photocatalytic applications—a review. Journal of Sol-Gel Science and Technology, 96(1), 1–14. doi:10.1007 / s10971-020-05333-9  Miklos, D. B., Remy, C., Jekel, M., Linden, K. G., Drewes, J. E., & Hübner, U. (2018). Evaluation of advanced oxidation processes for water and wastewater treatment – A 15 critical review. Water Research, 139, 118–131. doi:10.1016 / j.watres.2018.03.042  Moss, B., Lim, K. K., Beltram, A., Moniz, S., Tang, J., Fornasiero, P., … Kafizas, A. (2017). Comparing photoelectrochemical water oxidation, recombination kinetics and charge trapping in the three polymorphs of TiO2. Scientific Reports, 7(1), 2938. doi:10.1038 / s41598-017-03065-5 20  Samuel, O., Othman, M. H. D., Kamaludin, R., Sinsamphanh, O., Abdullah, H., Puteh, M. H., & Kurniawan, T. A. (2022). WO3–based photocatalysts: A review on synthesis, performance enhancement and photocatalytic memory for environmental applications. CeramicsInternational, 48(5), 5845– 5875.doi:10.1016 / j.ceramint.2021.11.158 25  Saravanan, A., Deivayanai, V. C., Kumar, P. S., Rangasamy, G., Hemavathy, R. V., Harshana, T., … Alagumalai, K. (2022). A detailed review on advanced oxidation process in treatment of wastewater: Mechanism, challenges and future outlook. Chemosphere, 308(Pt 3), 136524. doi:10.1016 / j.chemosphere.2022.136524  Saravanan, A., Senthil Kumar, P., Jeevanantham, S., Karishma, S., Tajsabreen, B., 30 Yaashikaa, P. R., & Reshma, B. (2021). Effective water / wastewater treatment methodologies for toxic pollutants removal: Processes and applications towards sustainable development. Chemosphere, 280(130595), 130595. doi:10.1016 / j.chemosphere.2021.130595  Surela, A. K., Chhachhia, L. K., Surela, V. K., & Meena, P. L. (2024). Polypyrrole-based 35 composites for dyes removal from contaminated water. In Reference Module 17 Materials Science and Materials Engineering. doi:10.1016 / b978-0-323-95486-0.00019- 3  Özel, Ş., & Kara, A. (2018). Photocatalytic magnetic polyfunctional Synthetic Reagent Blue 221 (RB 221) dye is applied to microspheres from aqueous solutions. Investigation of adsorption and kinetic parameters. International Journal of Life 5 Sciences and Biotechnology, 1(2), 84–95. doi:10.38001 / ijlsb.478214  Nikazar, M., Gholivand, K., & Mahanpoor, K. (2008). Photocatalytic degradation of azo dye Acid Red 114 in water with TiO2 supported on clinoptilolite as a catalyst Desalination, 219(1–3), 293–300. doi:10.1016 / j.desal.2007.02.035  PubChem. (2024). Acid Red 114. National Center for Biotechnology Information. 10 Retrieved from https: / / pubchem.ncbi.nlm.nih.gov / compound / Acid-Red-114  Rajeshwar, K., Osugi, M. E., Chanmanee, W., Chenthamarakshan, C. R., Zanoni, M. V. B., Kajitvichyanukul, P., & Krishnan-Ayer, R. (2008). Heterogeneous photocatalytic treatment of organic dyes in air and aqueous media. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 9(4), 171–192. 15

Claims

18 REQUESTS 1. Simultaneous removal of colored organic pollutants and residues from wastewater from industrial facilities. 5 Used in the treatment of wastewater through adsorption and photocatalytic decolorization processes These are magnetic hybrid adsorbent-photocatalyst composite particles with a polymer matrix, Its characteristics include benzoyl peroxide as an initiator, pure water as the dispersion phase, and as a stabilizer. Polyvinyl alcohol, 4-vinylbenzyl chloride as monomer, 1,2- as crosslinking agent. Bis(methacryloxy)ethane, Fe₃O₄ nanoparticles as magnetic core and It contains TiO₂ nanoparticles as a photocatalyst. 10 2. Magnetic hybrid adsorbent-photocatalyst composite particles conforming to Claim 1, Its composition includes 0.1-0.3% benzoyl peroxide by weight, and 75-84% pure water. 0.2-0.5% polyvinyl alcohol, 6-10% 4-vinylbenzyl chloride, 8-12% 1,2-Bis(methacryloxy)ethane, 0.5-1.5% Fe₃O₄ and 0.5-1.5% TiO₂ 15 It includes.

3. Magnetic hybrid adsorbent-photocatalyst composite particles conforming to Claim 1, Composition: 0.162% benzoyl peroxide, 80.873% pure water, 0.323% polyvinyl alcohol, by weight. 7,406% 4-vinylbenzyl chloride, 9,618% 1,2-Bis(methacryloxy)ethane, 0.809% Fe₃O₄ and 20% It contains 0.809 TiO₂.

4. Simultaneous removal of colored organic pollutants and residues from wastewater from industrial facilities. Used in purification through adsorption and photocatalytic decolorization processes. 25 of the polymer matrix magnetic hybrid adsorbent-photocatalyst composite particles It is a synthesis method, and its characteristic is; a. Distribution phase by stirring polyvinyl alcohol until it dissolves in pure water. preparation, b. Organic by mixing 4-vinylbenzyl chloride and 1,2-Bis(methacryloxyyl)ethane preparation of phase 30 c. Adding TiO₂ and Fe₃O₄ nanoparticles to the dispersion phase and mixing them, d. Distribution of the phase with added nanoparticles in the sonicator, e. Addition of the organic phase to the dispersion phase f. Reacting the mixture by suspension polymerization, 19 g. Washing and decanting of composite particles formed after the reaction. h. Drying the prepared particles and sieving the dried particles. It includes the steps of the process.

5. A method that complies with claim 4, characterized by: a. the mixing of polyvinyl alcohol and pure water in the process step. The dispersion phase is mixed in a heated magnetic stirrer at a speed of 400–1000 rpm. preparation.

6. A method that conforms to claim 4, and its characteristic is; in step b, 4-vinylbenzyl chloride and 1,2-10 Bis(methacryloxy)ethane is mixed in a heated magnetic stirrer at a speed of 400–1000 rpm. It is the preparation of the organic phase by mixing.

7. This is a method that complies with claim 4, and its characteristic is that in step c of the process, TiO₂ and are added to the Distribution phase. Fe₃O₄ nanoparticles were mixed in a heated magnetic stirrer at a speed of 400–1000 rpm for 15 minutes. It is added by mixing.

8. This is a method that complies with claim 4, and its characteristic is; suspension at step f. polymerization at a temperature of 55–65 °C for 4-24 hours It is the realization of. 20 9. A method that conforms to claim 4 or 8, and whose characteristic is; suspension at step f. The polymerization is carried out at a temperature of 60°C for 6 hours.

10. A method that complies with claim 4, and its characteristic is that the particles prepared in step h are 25 Drying is done at a temperature between 40–130 °C for 8–24 hours.

11. A method that complies with Claim 4, and its characteristic is that the dried particles are processed in step h. It is fractionated by sieving with sieves in the 45–500 µm range.

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