Synthesis and Characterization of Li2Mn0.8Ni0.2SiO4/Mn3O4 Nanocomposite for Photocatalytic Degradation of Reactive Blue (RB5) Dye

This study successfully synthesized Li2MnSiO4/Mn3O4 (LMS/M3) and Li2Mn0.8Ni0.2SiO4/Mn3O4 (LMNS/M3) nanocomposites in a two-step method first, by preparing Mn3O4 (M3) nanoparticles through a hydrothermal method and second, by synthesizing Li2MnSiO4 (LMS) and Li2Mn0.8Ni0.2SiO4 (LMNS) by ethylene diamine tetra-acetic assisted sol–gel method. In the last method, the two nanoparticles are mixed by hand-milling to form nanocomposites. Synthesized nanoparticles were characterized using X-ray diffraction, Fourier-transform infrared, Raman spectra, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, Brunauer–Emmett–Teller surface area, pL and UV–vis spectra measurements. The nanocomposite presents a well-developed orthorhombic crystal structure with a Pmn21 space group. BET surface area measurements indicate that all the prepared materials are mesoporous. The photocatalytic activity of M3, LMS, LMNS, (LMS/M3), and (LMNS/M3) was investigated by the photocatalytic degradation of reactive blue 5 (RB5) under UV light irradiation using a homemade photoreactor. The maximum photodegradation was achieved at optimal pH 4 and photocatalyst dose 0.005 g/50 ml dye. Higher stability for dye degradation efficiency was attained for the LMS and LMNS nanomaterials and LMS/M3 and LMNS/M3 nanocomposites than M3 to photocatalytic activity. The photocatalyst is readily recoverable and shows excellent stability even after three cycles. The photocatalytic degradation for RB5 followed first-order kinetics.


Introduction
One of the main causes of environmental pollution issues is the growing amount of textile wastewater that results from a growth in the demand for textile goods. The wastewater includes substances like dyes that pose danger to aquatic life [1][2][3][4]. Every year, 12% of the synthetic textile dyes used are turned into wastewater, and 20% of the losses will enter the environment via effluents of wastewater treatment plants [5]. Environmental cleanup is necessary for people to maintain a good quality of health. Organic dyes are Azo dyes are a broad and powerful class of synthetic dyes used in industrial settings. Reactive dyes are significant and vital groups because of their toxicity and aromatic constitution and cancer due to water pollution [6,7]. Reusing water is increasingly being endorsed as a method of increasing freshwater resources [8]. Therefore, it's crucial to find a treatment approach that is both efficient and economical to remove or decompose the dye that is present in wastewater [8][9][10]. In this context, numerous techniques have already been employed for dye removal from wastewater, including electrochemical technology, membrane, oxidation by ozone, coagulation/flocculation, photocatalysis, biological purification [11][12][13][14][15][16].
The most effective method is photocatalysis, which is economical because the photocatalyst can be recycled and reused. When exposed to light, materials with photocatalytic properties can generate electrons and holes, gaining promising photocatalysis components [17]. Photocatalysis is a method that is beneficial to the environment and has a number of benefits including; (1) it eliminates the need for auxiliary chemicals like ozone in the degradation of pollutants, (2) it operates at ambient conditions and (3) it converts harmful organic contaminants into harmless inorganic carbon dioxide and water through mineralization [18]. Manganese oxide catalysts can occur as MnO, MnO 2 , Mn 2 O 3 , and Mn 3 O 4 . Manganese oxide (hausmannite) is a crucial substance because of its unique chemical and physical features and low cost. It has potential applications in many fields such as magnetic and electrochromic materials, batteries, catalysts, etc [19]. The enhanced photocatalytic activity of Mn 3 O 4 is due to Mn vacancies inside the lattice and is best recognized for its catalysis in the oxidation process [20].
In recent years, the transition metal silicate compounds, Li 2 MSiO 4 (M = Fe, Mn, Co, Ni), have received increasing attention due to their advantages of high thermal stability, high capacity (330 mA h g −1 ), nontoxicity, and low cost. The Li 2 MnSiO 4 material produces the largest reversible capacity within a suitable voltage-stability window [21]. However, the low intrinsic electronic and lithiumion conductivities and poor cycling stability restrict its applicability. Many approaches have been devised to solve these issues, including ion substitution, particle size reduction, and carbon coating [22]. To solve the drawbacks, the Mn site was partially replaced with Mg, Al, or Fe to enhance the structural stability of Li 2 MnSiO 4 cathode materials [23]. Due to the similar valence of Ni 2+ to Mn 2+ , Ni 2+ was chosen in this study to take the place of the Mn 2+ sites in Li 2 MnSiO 4 , substituting Ni 2+ to Mn 2+ , would not result in a significant amount of crystalline deformation. Also, Mn 3 O 4 has been used as a coating material on the surface of Li 2 MnSiO 4 for the first time although there are several metal oxides have been used before such as TiO 2 [24], MoO 2 [25] and V 2 O 5 [26].
Based on the above consideration, we prepare and characterize the M3, LMS, and LMNS nanomaterials and the LMS/M3 and LMNS/M3 (95:5 wt%) nanocomposites. The prepared materials are characterized using different techniques, and the photodegradation of reactive blue 5 (RB5) using all samples is discussed in detail. We evaluated numerous conditions affecting the nanomaterials' degradation efficiency in aqueous solutions to determine the photocatalyst's degradation efficiency in various instances. This study estimated the effect of the photocatalyst dose (0.002, 0.005, and 0.01 g/50 ml), initial concentrations for RB5 (10, 20, 30, and 40 ppm), and the initial pH of dye solutions (3,4,6,8, and 10) on the photodegradation process. The first-order kinetic model was used to explore the RB5 photodegradation kinetics, and the kinetic rate constants were estimated and compared.

Mn 3 O 4 Nanomaterial Synthesis
Mn 3 O 4 nanomaterials were synthesized according to the literature [27] with a small modification via 0.02 mol KMnO 4 dissolved in 100 ml deionized water, followed by adding ethylene glycol (20 ml) dropwise under stirring continuously for an hour. The suspension was transferred to a Teflonlined autoclave with a 125-ml capacity and heated under pressure for 4 h at 140 °C. The autoclave was then cooled to room temperature, and the precipitate obtained was washed several times with deionized water, dried at 80 °C, and the final product was transferred to a muffle furnace and ignited at 300 °C for 4 h to remove impurities. After cooling, it was ground by an agate mortar to obtain a refined product, denoted as M3 (Fig. 2a).

Characterization
X-ray diffraction (XRD) on a high-resolution PAN analytical diffractometer was used to monitor the crystalline structure of the synthesized M3, LMS, LMNS, LMS/M3, and LMNS/ M3 nanomaterials. CuKα radiation was used to record the scans at a voltage of 40 kV from 10° to 80° 2θ angles. The Fourier-transform infrared (FTIR) spectra measurements were performed using a single beam Thermo scientific Nicolet iS 10. The measurements were recorded within a 4000-400 cm −1 region. A Raman spectrometer (Renishaw brand-via Raman, with an excitation laser line of 632.8 nm from a He-Ne laser) was used to measure the Raman. The surface morphology and elemental mapping analyses were examined using energy-dispersive X-ray spectrometry (EDS) linked to scanning electron microscopy (SEM) Zesis operating at 5 kV. The crystal structure was investigated by transmission electron microscopy (TEM) JEOL JEM-1400. The surface area and pore size diameter were determined at 77 K using a typical volumetric apparatus (Quantachrome NOVA automated) and the N 2 adsorption isotherm technique. A 320 nm (140 W) excitation laser (Jobin Yvon HORIBA TRIAX 190 spectrometer) was used to gather the photoluminescence spectra. The synthesized materials' band gap energy was accessed and measured using UV-vis diffuse reflectance spectra (UV-vis, Perkin-Elmer Lambda 950).

Photodegradation of RB5
Typically, prepared nanomaterials were examined for the photodegradation of 50 ml RB5 aqueous solution with different initial concentrations (10,20,30, and 40 ppm), pH dye solutions (3, 4, 6, 8, and 10), and catalyst doses (0.002, 0.005, and 0.01 g/50 ml). An adsorption-desorption equilibrium was achieved by agitating the suspension using a magnetic stirrer for 60 min at room temperature and in the dark. The suspension was placed in a homemade photoreactor and exposed to UV light (a mercury lamp) for 0-120 min. At specific time intervals, 3 ml of the suspension was taken using a syringe and centrifuged thoroughly to extract the photocatalyst. The photodegradation (%) was determined by measuring the absorption of RB5 in the filtrate at its maximum wavelength (λ max = 670 nm) using a UV-vis absorption spectrophotometer. Experiments were used to study photodegradation because numerous variables affect the system's photocatalytic activity.

Point of Zero Charge (PZC)
All synthesized samples' PZC values were calculated using Naeem et al.'s method [29]. This method is applied by preparing 50 ml of 0.01 M KNO 3 solution in a separate vessel over a pH of 3.0-10.0, where the initial pH was adjusted using 0.1 N HCl and 0.1 N NaOH solutions. After controlling the pH of 0.01 M KNO 3 at 3.0-10.0, 0.005 g of each photocatalyst was added to different vessels. These suspensions were shaken for 2 h and left for 2 days, after which they were filtrated and repeated to measure the final pH value.

XRD
XRD was used to determine the crystallinity of all synthesized nanomaterials. Figure 3a shows the XRD pattern of the M3 powdered sample, which demonstrates peaks at 17 [27,30]. Figure 3b and c show the XRD pattern of the LMS and LMNS materials at a 2θ range of 10-80°. The sharp peaks were positioned at 16.47°, 24.31°, 28.22°, 33.02°, 36.14°, 37.66°, 46.73°, 59.19°, and 65.71°, indicating the good crystallinity of the synthesized material with an orthorhombic Pmn2 1 phase structure. Some impurities were observed, such as Li 2 SiO 3 and MnO [31]. These impurities are frequently reported to coexist with the Li 2 MnSiO 4 therefore, preparing pure-phase Li 2 MnSiO 4 is challenging [32].
Although Li 2 MnSiO 4 has extensive polymorphism, the orthorhombic structure Pmn2 1 is the most frequently observed because the Li-ion transfer inside the host material will be quick due to the lower migration energy barrier and symmetrical equivalency of the Li sites in the unit cell, especially for materials with nano-dimensions. These findings are consistent with the literature [33]. Scherrer's formula Eq. (1) was used to calculate the average crystallite size for all prepared materials from the Bragg peak (Table 1).
The diffraction pattern of the LMS/M3 and LMNS/M3 composites is the same as that of the LMS nanomaterial (Fig. 3d, e), indicating that the Mn 3 O 4 nanoparticles did not affect the crystal structure of Li 2 MnSiO 4 . The diffraction peaks of the Mn 3 O 4 nanoparticles do not appear in the nanocomposites' patterns, indicating the diffraction intensity of the nanoscale Mn 3 O 4 with a concentration of 5.0 wt% is too small compared with the intensity of the LMS and LMNS nanocomposite patterns [26].

FTIR Analysis
The FTIR spectra provided a large amount of qualitative information to identify the produced nanomaterials (Fig. 4).
In the 400-650 cm −1 region of the Mn 3 O 4 nanomaterial's spectrum ( Fig. 4a), three prominent peaks appeared. The vibrational peak at 418 cm −1 is associated with the vibration of manganese species (Mn 3+ ) in the octahedral site of Mn 3 O 4 [34]. The vibration frequency at 488 cm −1 is associated with the distortion vibration of Mn-O in an octahedral environment, and the third vibration frequency at 601 cm −1 is a feature of Mn-O stretching modes in tetrahedral sites [35]. This result further proved that the prepared compound was Mn 3 O 4 . Figure 4b and c show that for LMS and LMNS, the O-Li-O bending vibration of LiO 4 tetrahedra corresponds to the vibrational peak of 420 cm −1 [31] The vibrational peaks in the 480-590 cm −1 band represent the O-Si-O bending vibrations, whereas the vibrational peaks in the 860-927 cm −1 band represent the stretching vibrations of the Si-O bonds in SiO 4 tetrahedra [32]. The peaks above 1000 cm −1 could be attributed to the C-O from the impure phase [36]. Figure 4d and e show the FTIR spectra of LMS/M3 and LMNS/M3 exhibiting the same spectrum as LMS. Furthermore, the intensity peaks in the LMS/M3 and LMNS/M3 spectra at 400-650 cm −1 are slightly broadening, especially at 610 cm −1 , indicating a strong interaction between the moieties forming the sample. These outcomes indicate the successful synthesis of LMS/M3 and LMNS/ M3 nanocomposites.

Raman Spectroscopy
We used Raman spectroscopy to assess the types and relative amounts of graphene and carbon produced on the nanoparticle surface in the prepared materials (Fig. 5). Figure 5a shows the Raman spectrum of M3 nanoparticles. From group theory, Hausmannite Mn 3 O 4 (MnO·Mn 2 O 3 in spinal notation) is a standard tetragonal spinal structure  . Therefore, the breathing mode of the tetrahedral units primarily influences this unit's bonding and repulsion effects, i.e., the covalency of Mn-O bonds [35]. Figure 5b-e show the Raman spectra of LMS, LMNS, LMS/M3, and LMNS/M3, respectively. Two significant peaks at 1355 and 1600 cm −1 corresponding to the fundamental D and G bands of carbons, respectively, can be found in the spectra of LMS, LMNS, LMS/M3, and LMNS/M3. The G band denotes the presence of graphitized carbon, whereas the D band is linked to disordered carbon or faults in the graphene layers. A helpful index for determining the level of ordering in carbon materials is the peak intensity ratio between the D and G bands (I D /I G ), with a lower value of I D /I G related to a higher order level. The LMS, LMNS, LMS/M3, and LMNS/M3 samples have I D /I G values of 0.887, 0.740, 0.789, and 0.704, respectively [21]. The findings revealed that the synthesized LMNS/M3 had good electronic conductivity because a lower ID/IG suggests better carbon electronic conductivity [37].  Figure 6a shows SEM images of the M3 sample, showing that the preparation of octahedral crystals was adequate. The high-magnification photos illustrate the octahedral crystals' completeness, sharpness, and point angles. The yield of Mn 3 O 4 octahedrons is very high, and most crystals have highly octahedral morphology [38]. Figure 6b and c show the SEM images of nanomaterials LMS and LMNS. The powders from the two samples comprise aggregated nanoparticles. The primary particle diameter of Li 2 MnSiO 4 ranges from 30 to 50 nm. The particle size is reduced via nickel doping, and the LMNS powder's primary diameter is 15-30 nm. Additionally, the LMNS powder has a more homogenous particle distribution than LMS [39]. Figure 6d and e show SEM images of LMS/M3 and LMNS/M3 nanocomposites mixed with the constituent materials, which shows a significant decrease in the particle size [30] and the octahedron of Mn 3 O 4 particles distributed on the surface of the LMS and LMNS particles. Figure 6f-j show the nanomaterials' elemental compositions from the EDS. Figure 6f shows the EDS of as-made M3, and Mn and O are present in the produced nanoparticles, according to the EDS spectrum data. No other EDS peak connected to any contaminant has been found [40]. Figure 6g-j shows the EDS spectra of LMS, LMNS, LMS/M3, and LMNS/M3, respectively. All expected elements in all investigated nanomaterials were observed (Table 2). However, the small percentage of carbon in the samples could be due to some impurities from the furnace.

TEM Analysis
The morphological features of the M3, LMS, LMNS, LMS/ M3, and LMNS/M3 materials are examined and exhibited using TEM (Fig. 7). Figure 7a is the TEM image of the M3, confirming that octahedral crystals have been successfully prepared with a particle size 20 nm [38], correlating well with the XRD and SEM results.   Figure 7b and c show the TEM images for LMS and LMNS and that they comprise various nanoparticles from 40 to 100 nm and show clear signs of aggregation [41]. As seen from TEM images of Fig. 7d and e, the average sizes of LMS/M3 and LMNS/M3 nanoparticles in the composite are 50-20 nm. It is suggested that introducing Mn 3 O 4 to the Li 2 MnSiO 4 will decrease the particle size, correlating well with XRD and SEM data. Figure 8 shows the N 2 adsorption-desorption isotherms of the investigated specimens. Table 3 summarizes the BET surface areas (S BET ) and average pore sizes of the synthesized nanomaterials, corresponding to the IUPAC adsorption isotherm system. Figure 8a illustrates the N 2 adsorption-desorption isotherms of Mn 3 O 4 . It demonstrates a capillary condensation step at a relative pressure between 0.85 and 0.98, which might be specified by a hysteresis loop. This behavior typically occurs in mesoporous adsorption. According to the IUPAC isotherm system, the hysteresis loop corresponds to the H3 type. This system also demonstrated that the adsorption volume increases with pressure and is unlimited at reasonably high pressures. This hysteresis loop typically presents in materials with long, narrow porous structures. The BET surface area of the sample is 20.7 m 2 /g, much higher than the commercial Mn 3 O 4 crystals (1 m 2 /g), and the pore distribution lies in the range of 1-5 nm, with a maximum of 1.5 nm [30].

PL Analysis
The efficiency of photogenerated electron-hole separation and transmission of the holes from the interior to the exterior surfaces are directly connected to photocatalytic activities. The recombination of free carriers is the source of the photoluminescence spectrum. PL emission spectra are widely used to examine the effectiveness of charge carrier immigration, transfer, and trapping and realize what happens to photogenerated electrons and holes in semiconductors. Lower PL intensity indicates longer photogenerated electron and hole lifetimes [43]. Figure 9a-e show the PL emission spectra of the M3, LMS, LMNS nanomaterials and LMS/M3 and LMNS/M3 nanocomposites at room temperature obtained by exciting using a 320 nm light. It is discovered that the intensity of the PL peak decreases in the order of the reduction in the PL peaks' intensity of the LMNS/M3 and LMS/M3 hetero junctions indicates that photogenerated charge carriers'

Optical Property of Synthesized Materials
Using UV Visible diffuse reflectance spectroscopy, the band gap energies of the prepared nanomaterials were calculated from their UV-vis absorption spectra. Predicting the photophysical and photochemical properties of materials is particularly interested in this optical attribute. The Tauc plot of all prepared nanomaterials were drawn using the absorption data obtained by DRS spectroscopy under the presumption that the energy-dependent absorption coefficient (α) can be expressed as Eq. (3).
where B is a constant, h is the Planck constant, E g is the band gap energy, υ is the photon's frequency and. γ factor depends on the nature of the electron transition and is

PZC
The PZC can determine the pH at which the electrical charge density is zero (pH PZC ). The charge on the surface is negative above (pH PZC ) and positive below. The PZC for synthesized Mn 3 O 4 nanoparticles is pH 4.5, correlating well with the literature [44], and the PZC values for LMS and LMNS nanomaterials and LMS/M3 and LMNS/M3 nanocomposites are 5.3, 5.4, 5.2, and 4.9, respectively, demonstrating that following its contact with the LMS and LMNS, the PZC of the Mn 3 O 4 nanomaterial was pushed toward a high pH value (Fig. 11).

Photocatalytic Degradation Studies
Under UV irradiation (mercuric lamp), the nanomaterials' photocatalytic degradation activity was evaluated under ideal conditions on 50 ml of a 20 ppm RB5 dye solution.
The effects of pH, dye concentration, and photocatalyst dose were investigated on the samples. The dye solutions were agitated for an hour in the dark before being exposed to UV light to reach adsorption-desorption equilibrium between the RB5 molecules and the catalyst's surface.

Photocatalyst Dosage Effects
Experiments were conducted using various photocatalyst dosages (0.002, 0.005, and 0.01 g/50 ml), with a constant dye concentration of 20 ppm/50 ml at 25 °C at pH 4 as (Fig. 12) to examine the impact of photocatalyst dosage on the dye degradation. All nanomaterial samples were used by UV radiation throughout the trials. Due to an increase in the active sites available on the catalyst's surface, the dye degradation percentage rose with an increase in the photocatalyst dose [8]. Additionally, at catalyst loadings of 0.005 and 0.01 g/50 ml, the dye degradation is similar after a specific period. This observation could be because, as the catalyst loading is increased above 0.005 g/50 ml, the number of photocatalyst-accessible active sites decreases due to photocatalyst particle aggregation, reducing the need for additional catalysts to support catalytic activities. Therefore, the optimal catalyst loading for further studies has been determined as 0.005 g/50 ml [18].

Dye Concentration Effects
With a catalyst dose of 0.005 g/50 ml dye solution, pH 4 for 120 min., the impact of the initial dye solution's   ppm. According to Fig. 13, the percentage of dye degradation reduces as the dye's initial concentration increases when exposed to UV radiation. The degradation percentage depends on the likelihood that hydroxyl radicals ( · OH) will form on the catalyst surface and interact with the dye molecules [45]. The catalyst requirement and irradiation time increase as the initial dye concentration rises [46]. The proportionate production of · OH and superoxide radical anions on the catalyst surface decrease due to the constant irradiation time and catalyst amount, decreasing photocatalytic degradation efficiency [9].

pH Effects
The pH range of dye effluents released into the environment is typically vast and affects how easily · OH develops during photodegradation. Since photocatalysis degrades dye molecules, pH is crucial. Numerous attempts have been conducted in this direction because evaluating the pH influence is crucial in dye degradation [47]. When the medium's pH changes toward an acidic or basic scale, the degradation occurring at a neutral pH varies significantly [17]. Furthermore, anionic dyes are weak acids with many sulphonate functional groups (-SO 3 − ) that prefer negatively charged dye molecules [48]. Solutions of 0.1 M NaOH and 0.1 M HCl were used to modify pH values of 3, 4, 6, 8, and 10 (Fig. 14a). The dye degradation increased to 96.7%, 61.8%, 65.6%, 70.1%, and 74.4% for the M3, LMS and LMNS nanomaterials, and LMS/M3 and LMNS/M3 nanocomposites at pH 4. When the pH is acidic, the catalyst has positive charges on its surface and a stronger electrostatic attraction to the anionic dye species, whereas the catalyst has a negative charge on its surface and repels the anionic dye when the pH is basic. This result explains how degradation efficiency changes at various pH levels. The optimal pH was chosen as pH 4 for further studies.

Kinetics of Dye Degradation
The rate-constant values (k 1 ) of the degradation reaction were calculated from the slope of linear regression obtained from the kinetic plot of ln (A/A 0 ) versus time using the following Langmuir-Hinselhood equation, where A 0 and A are the initial concentration and concentration of the dye solution at time t [49]. The straight line obtained from the plots confirms that the degradation of RB5 followed first-order kinetics for all samples' dye concentrations ( Fig. 14b-f). Table 4 lists the correlation coefficient (R 2 ) and the rate-constant of all photocatalysts under UV irradiation. The rate-constant values of LMNS/M3 and LMS/M3 are higher than pure LMNS and LMS, respectively, indicating that prepared nanocomposites are the more active catalyst due to M3 coating on the LMNS or LMS surfaces, and the kinetic models of the various catalyst were studied at optimum conditions (Table 5).

The Proposed Mechanism of Photodegradation of RB5 Under UV Irradiation
For a conventional semiconductor photocatalyst, the produced electrons and holes might immediately break down contaminants. The highest photocatalytic degradation

Reusability of the Photocatalysts
Through three recycling studies for the photodegradation of RB5 under simulated UV irradiation under the same optimum reaction parameters, the reusability of the M3, LMS, LMNS nanomaterials, and LMS/M3, LMNS/M3 nanocomposites was evaluated as an important factor for the practical applications. The photocatalysts were employed in the subsequent cycle after being cleaned with deionized water, centrifuged and dried in an oven at 80 °C and centrifuged. The results as shown in Fig. 16 demonstrate that after two cycles, degradation efficiency of synthesized nanomaterials was observed to be reduced. The loss of the distinct catalyst throughout the recovery phase may be responsible for the slight decrease in the degradation efficiency. Therefore, the present work of the degradation efficiency is significantly compared with previously reported works in literature (Table 6).

Conclusion
Novel LMNS/M3 and LMS/M3 nanocomposites were synthesized by preparing pure LMNS and LMS using ethylene diamine tetra-acetic assisted sol-gel method and synthesizing M3 using the hydrothermal method. Synthesized nanoparticles were characterized using XRD, FTIR, Raman spectra, SEM, EDS, TEM, BET surface area, pore size distribution, PL, and UV-vis spectra measurements. XRD analysis confirmed that M3 was crystallized in the tetragonal phase, and LMS, LMNS, LMS/M3, and LMNS/M3 have a good crystallinity of the synthesized material with an orthorhombic Pmn2 1 phase structure. The synthesized samples' crystal sizes were calculated using the Scherer equation from XRD data. The particles' morphology was observed in SEM and TEM images, and the particles were nanoscale in size. BET surface area measurements indicate that all the prepared materials are mesoporous. These materials were used to examine the photocatalytic degradation properties of RB5. Many parameters affecting dye photodegradation using all created nanomaterials were   Data Availability All the datasets used and/or analyzed in thisstudy are available in the manuscript and supplementary information can beasked from the corresponding author upon request.

Competing Interests
The authors declare no competing interests.
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