Synthesis of the ZnTiO3/TiO2 Nanocomposite Supported in Ecuadorian Clays for the Adsorption and Photocatalytic Removal of Methylene Blue Dye

Currently, the study of semiconductor materials is very promising for the photocatalytic remediation of hazardous organic substances present in the air and water. Various semiconductors have been investigated in this interesting photo-assisted methodology, among them metal oxides such as ZnO, TiO2 and their derivatives. In this study, ZnTiO3/TiO2 was synthesized by the sol-gel method using Ti(OC3H7)4 and Zn(CH3COO)2 · 2H2O as reagents. The role of several conditions such as synthesis temperature and TiO2:ZnO proportion on the morphology and purity of compounds obtained was studied, and the suitable conditions for the synthesis of photocatalysts were determined. Various techniques were used to conduct a systematic investigation on the structural, morphological, and photocatalytic properties of ZnTiO3/TiO2. Scanning Electron Microscopy (SEM) images show that ZnTiO3/TiO2 have a typical particle size of approximately 100 nm with a quasi-spherical shape. The adsorption and photocatalytic activity were investigated by the decolorization of Methylene Blue (MB) as an organic contaminant under UV irradiation both in TiO2 and ZnTiO3/TiO2 supported over some Ecuadorian clays. The materials evaluated were prepared in the shape of 0.2 cm (diameter) and 1.0 cm (length) cylindrical extrudates. The degradation percentage of MB obtained was 85% approximately after 150 min of irradiation. The results obtained allow us to conclude that these synthesized materials can be used as adsorbents and photocatalysts.


Introduction
The presence of pollutants in wastewater has a dangerous potential impact on the environment and on health. In fact, water and wastewater treatment is a major problem in our society [1]. Several industries use large amounts of dyes for their end-products. For instance, the textile industry uses more than 10,000 types of dyes. This industry discharges 2% to 20% of its dyes as aqueous effluents [2]. Many of these substances are not biodegradable and pollute the aquatic environment [3], and some of them have a carcinogenic effect [4]. Hence, it is necessary to treat the effluents before discarding them.
There are several technological processes to remove persistent pollutants from water [1,[5][6][7][8]. Among these processes, photocatalysis is appreciated for its effectivity [9,10]. Photocatalysis is an Advanced Oxidation Process (AOP) that requires a semiconductor [11] that interacts with photons and the adsorbed composite through surface charges. The interaction produces radical species that decompose the adsorbed composite through redox reactions [12]. a hydrochloric acid solution (0.1 N) at the ratio of 10 mL/g. The organic matter in the clay samples was removed by oxidation using H 2 O 2 (33%) in the proportion of 10 mL of H 2 O 2 for each gram of clay. The samples were constantly stirred for 2 h at room temperature. Subsequently, the samples were centrifuged and washed with distilled water to eliminate Cl − ions, which was verified with a test with AgNO 3 . The clay adsorption sites were activated with nitric acid (0.8 N) using a ratio of 10 mL/g. Activation is a process through which a partially dissolved material is obtained, which has greater surface acidity, porosity, and surface area [37]. The activated clay samples were centrifuged, washed with distilled water, and dried at 60 • C for 24 h.

Synthesis of the ZnTiO 3 /TiO 2 -Clay Composite
The ZnTiO 3 /TiO 2 photocatalysts were synthesized following a modified sol-gel method described for other nanocomposites [38,39]. Several TiO 2 /ZnO molar ratios were tested (9:1, 4:1, 3:1, and 2:1). Different calcination temperatures (500, 600, 700, 800, 900, and 1000 • C) were also tested to obtain the optimal photocatalyst synthesis conditions. Afterwards, the synthesis process was repeated in a clay solution as follows: Clay (1 g) was dissolved in isopropyl alcohol (iPrOH) (10 w/w%) under stirring for 24 h to achieve homogenous solution. Subsequently, a quantity of titanium (IV) isopropoxide (TiPO) in iPrOH (70 v/v%) was added to the solution at room temperature, using a ratio of 10.5 mmol of Ti per gram of clay. Previously, a solution formed by Zn(acet), water, and iPrOH was slowly added, using the optimal ZnO/TiO 2 molar ratio. The amount of water had a 50 v/v% iPrOH/water ratio and was determined by stoichiometry, being the amount necessary to hydrolyze the TiPO molecules. The synthesis was performed at room temperature. The reaction system was additionally stirred for 30 min. The mixture was kept under stirring at room temperature for another 30 min after the formation of a precipitate. The precipitate was dried at 60 • C for 24 h and calcined at the optimum temperature for 4 h. Finally, the products were cooled at room temperature. To obtain clay supported TiO 2 , the procedure described above was repeated for a final ratio of 10.5 mmol Ti per gram of clay but without the addition of ZnO.

Preparation of the Supported Photocatalysts
For the evaluation of the solid materials, cylindrical extrudates with approximate dimensions of 0.2 cm in diameter and 1.0 cm in length were prepared. The preparation of these solids was carried out by mixing the solid materials with water (approximately 35%) to form a mixture with good plasticity. This mixture was extruded with a 2.5 mm diameter syringe. The extrudates were dried at 90 • C for 2 h and finally calcined at 500 • C for 8 h.

Characterization
The synthetized materials were characterized using a JEOL JSM 6400 scanning electron microscope (SEM) (JEOL, Peabody, MA, USA). X-Ray Fluorescence (XRF) measurements were recorded in a Bruker S1 Turbo SDR portable spectrometer (Bruker Handheld LLC, Kennewick, WA, USA), using the Mining Light Elements measurement method. The X-ray diffraction (XRD) measurements were recorded in a Bruker-AXS D8-Discover diffractometer (Bruker AXS, Karlsruhe, Germany) equipped with a vertical θ-θ goniometer, a parallel incident beam (Göbel mirror), and a HI-STAR General Area Diffraction Detection System (GADDS) (Bruker AXS, Karlsruhe, Germany). The X-ray diffractometer was operated at 40 kV and 40 mA to produce the Cu Kα radiation (1.5406 Å). Data were recorded from 5-70 • in the 2θ range. The identification of the crystal phases was obtained by comparison of the XRD profile with the ICDD (International Centre for Diffraction Data, release 2018) database. The determination of the specific surface area of the solids (m 2 /g) was carried out in the ChemiSorb 2720 equipment (Micromeritics, Norcross, GA, USA), by nitrogen adsorption at the temperature of liquid nitrogen (−196 • C) with a 30% gas mixture of N 2 diluted in He. UV-Vis diffuse reflectance spectrum (DRS) of the photocatalysts were obtained on an UV-Vis spectrophotometer Thermo model: Nicolet Evolution 201/220 (ThermoFisher, Waltham, MA, USA), equipped with an integration sphere unit using BaSO 4 as Nanomaterials 2020, 10, 1891 4 of 20 reference. The Chemisoft TPx System (version 1.03; Data analysis software; Micromeritics, Norcross, GA, USA, 2011) allowed to calculate the specific surface area using the BET equation and the single point method.

Adsorption and Photocatalytic Degradation
Heterogeneous photocatalysis experiments were firstly performed at free pH = 8.0 during 150 min, varying the methylene blue solution concentrations (50,25,10, and 5 mg/L) and catalyst concentrations (100, 250, and 500 mg/L). In addition, the effect of the ZnO:TiO 2 molar ratio was examined to select the best catalyst. All the experiments were started with a 30 min adsorption step under dark conditions to obtain the adsorption-desorption equilibrium.
The photocatalytic activity of the compounds was evaluated by the photocatalytic degradation of methylene blue under solar light radiation. Solar light was simulated by a solar box equipped with an air-cooled 1500-W Xenon lamp (Atlas Material Testing Technology, Mount Prospect, IL, USA), which allows 300-800 nm wavelengths to pass through (ATLAS, SUNTEST CPS+). Irradiance was set to 250 W/m 2 . The photocatalytic activity of the compounds was also evaluated by the decolorization of methylene blue under UV-C (254 nm) light radiation to improve the photocatalytic degradation of MB [40].
Typically, 25 mg of catalyst were magnetically stirred in a methylene blue aqueous solution (MB) (100 mL of water containing 5 mg/L methylene blue). The solution was maintained in dark conditions for 30 min. Then, the suspensions were irradiated using solar or UV-C light (100 W germicidal UV-C). The temperature of the photoreactor (25 • C) was controlled throughout the reaction using a cooling circulator air system. The tests were carried out without adjusting the pH = 8.0. The remaining concentrations of methylene blue were determined at 623 nm using a Jenway 7350 spectrophotometer (Cole-Parmer, Staffordshire, UK). The MB removal rate was calculated by absorbance according to the Beer-Lambert law. Samples were drawn at 5 min intervals with a syringe and filtered through a 0.45 µm membrane filter to remove any solid particles interfering with the measurement. All tests were carried out in triplicate using a methylene blue solution blank irradiated with solar or UV-C light to eliminate any photolysis effect due to the light. The decolorization rate was better when using UV-C light for the selected operating conditions; in this way, the tests with the photocatalysts supported on clays were carried out under UV-C light.
The adsorption capacity of the synthetized materials was evaluated by the removal of methylene without light irradiation, using the same protocol that was used during the photocatalytic test.

Reuse of the Supported Photocatalysts
A recycle experiment on photocatalytic degradation of MB by ZnTiO 3 /TiO 2 -Clay, and TiO 2 /Clay was designed to determine the recycling property of these composites. After completing a treatment cycle, the catalysts extrudates were left in quiescent conditions for 60 min to achieve their precipitate. Then, the clear solution was removed from the reaction system and 100 mL fresh MB solution (5 mg/L) was injected into the reaction system, starting the next cycle. The recycle experiment was carried out for five cycles. Each cycle lasted 150 min under UV-C irradiation.            The crystalline sizes of powder samples prepared at 500 • C with the molar ratio of TiO 2 /ZnO (3:1) were calculated based on the main peak using the well-known Scherrer equation [41]:

Characterization of the Samples
where K is the shape factor (here, K = 0.89), λ is the wavelength of the X-ray beam used (here, λ = 0.15406 nm), θ is the Bragg angle, and β is the full width at half maximum (FWHM) of the X-ray diffraction peak, which was calculated using MDI JADE, version 6; Computer software, Materials Data Inc., Livermore, CA, USA, 2014. The average crystalline size of the phases present in the ZnTiO 3 /TiO 2 composite were 33.79 (±3.67) and 21.47 (±3.91) nm for ZnTiO 3 and TiO 2−a , respectively. Figure 3 shows the SEM image of the ZnTiO 3 /TiO 2 heterostructure synthesized with a TiO 2 :ZnO molar ratio of 3:1 and calcined at 500 • C. The image shows that the particles have an average particle size of 100 nm, are almost spherical and highly agglomerated. The crystalline sizes of powder samples prepared at 500 °C with the molar ratio of TiO2/ZnO (3:1) were calculated based on the main peak using the well-known Scherrer equation [41]:

SEM-EDX Analysis
where K is the shape factor (here, K = 0.89), λ is the wavelength of the X-ray beam used (here, λ = 0.15406 nm), θ is the Bragg angle, and β is the full width at half maximum (FWHM) of the X-ray diffraction peak, which was calculated using MDI JADE, version 6; Computer software, Materials Data Inc., Livermore, CA, USA, 2014. The average crystalline size of the phases present in the ZnTiO3/TiO2 composite were 33.79 (±3.67) and 21.47 (±3.91) nm for ZnTiO3 and TiO2−a, respectively. Figure 3 shows the SEM image of the ZnTiO3/TiO2 heterostructure synthesized with a TiO2:ZnO molar ratio of 3:1 and calcined at 500 °C. The image shows that the particles have an average particle size of 100 nm, are almost spherical and highly agglomerated.     The crystalline sizes of powder samples prepared at 500 °C with the molar ratio of TiO2/ZnO (3:1) were calculated based on the main peak using the well-known Scherrer equation [41]:

SEM-EDX Analysis
where K is the shape factor (here, K = 0.89), λ is the wavelength of the X-ray beam used (here, λ = 0.15406 nm), θ is the Bragg angle, and β is the full width at half maximum (FWHM) of the X-ray diffraction peak, which was calculated using MDI JADE, version 6; Computer software, Materials Data Inc., Livermore, CA, USA, 2014. The average crystalline size of the phases present in the ZnTiO3/TiO2 composite were 33.79 (±3.67) and 21.47 (±3.91) nm for ZnTiO3 and TiO2−a, respectively. Figure 3 shows the SEM image of the ZnTiO3/TiO2 heterostructure synthesized with a TiO2:ZnO molar ratio of 3:1 and calcined at 500 °C. The image shows that the particles have an average particle size of 100 nm, are almost spherical and highly agglomerated.

Optical and Photoelectric Properties
The optical absorption properties of photocatalysts can be characterized using the UV-visible (UV-vis) DRS in the range of 200-700 nm and at room temperature. Figure 5a shows the UV-vis XRD of ZnTiO 3 /TiO 2 and TiO 2 . Compared to TiO 2 , the visible light absorption intensity of ZnTiO 3 /TiO 2 , at around 400 nm, was improved, suggesting that the ZnTiO 3 /TiO 2 composite has a better response to visible light. The graphs of (αhv) 2 versus hv for calculating the direct band-gap energy (E g ) are shown in Figure 5b. According to Equation (2) [42], the direct E g values were 3.07 and 3.12 eV for ZnTiO 3 /TiO 2 and TiO 2 , respectively. The direct E g value calculated for ZnTiO 3 /TiO 2 can be related to the direct band gap of hexagonal or cubic ZnTiO 3 compound [43].
where E g is the band-gap energy in the electron volts (eV) and λ represents the lower cutoff wavelength in nanometers (nm).
Nanomaterials 2020, 10, x FOR PEER REVIEW 7 of 22 The optical absorption properties of photocatalysts can be characterized using the UV-visible (UV-vis) DRS in the range of 200-700 nm and at room temperature. Figure 5a shows the UV-vis XRD of ZnTiO3/TiO2 and TiO2. Compared to TiO2, the visible light absorption intensity of ZnTiO3/TiO2, at around 400 nm, was improved, suggesting that the ZnTiO3/TiO2 composite has a better response to visible light. The graphs of (αhv) 2 versus hv for calculating the direct band-gap energy (Eg) are shown in Figure 5b. According to Equation (2) [42], the direct Eg values were 3.07 and 3.12 eV for ZnTiO3/TiO2 and TiO2, respectively. The direct Eg value calculated for ZnTiO3/TiO2 can be related to the direct band gap of hexagonal or cubic ZnTiO3 compound [43].
where Eg is the band-gap energy in the electron volts (eV) and λ represents the lower cutoff wavelength in nanometers (nm). In order to analyze the photocatalytic mechanism of ZnTiO3/TiO2 heterojunction, the potentials of the Valencia Band (VB) and Conduction Band (CB) of TiO2 and ZnTiO3 were determined, which are important to estimate the flow diagram of pairs of photoexcited charge carriers in heterojunction. The Mulliken electronegativity theory was used to calculate the VB and CB potentials of TiO2 and ZnTiO3 [41]: where ECB and EVB are the CB edge potential and VB edge potential, respectively, Eg is the band gap energy of the semiconductor, Ec is the energy of free electrons on the hydrogen scale (approximately 4.5 eV), and χ is the electronegativity of the semiconductor. The values of ZnTiO3 and TiO2 were 4.0 and 5.8 respectively. According to the formula above, ECB and EVB for ZnTiO3 and TiO2 were (−0.22, +2.84) eV and (−2.06, +1.06) eV, respectively. Figure 6 describes the photocatalytic mechanism of the ZnTiO3/TiO2 heterojunction. In order to analyze the photocatalytic mechanism of ZnTiO 3 /TiO 2 heterojunction, the potentials of the Valencia Band (VB) and Conduction Band (CB) of TiO 2 and ZnTiO 3 were determined, which are important to estimate the flow diagram of pairs of photoexcited charge carriers in heterojunction. The Mulliken electronegativity theory was used to calculate the VB and CB potentials of TiO 2 and ZnTiO 3 [41]: where E CB and E VB are the CB edge potential and VB edge potential, respectively, E g is the band gap energy of the semiconductor, E c is the energy of free electrons on the hydrogen scale (approximately 4.5 eV), and χ is the electronegativity of the semiconductor. The values of ZnTiO 3 and TiO 2 were 4.0 and 5.8 respectively. According to the formula above, E CB and E VB for ZnTiO 3 and TiO 2 were (−0.22, +2.84) eV and (−2.06, +1.06) eV, respectively. Figure 6 describes the photocatalytic mechanism of the ZnTiO 3 /TiO 2 heterojunction. It was clear that the CB edge of TiO2 was more negative than the CB edge of ZnTiO3; on the other hand, the VB edge of ZnTiO3 was more positive than the VB edge of TiO2. Consequently, the electrons excited from the CB of TiO2 jumped to the CB of ZnTiO3, and the holes generated from the VB of ZnTiO3 transferred to the VB of TiO2, which caused an efficient separation of e − and h + , and the photocatalytic activity improved due to the ZnTiO3/TiO2 heterojunction [27,44,45].

XRF Analysis
Clays are minerals that are widely distributed in nature, being produced by the erosion of rocks. The texture and chemical composition of the clays are greatly varied, depending on the presence of organic and inorganic impurities as well as the geological origin of the clays. Table 1 shows the composition of the clays used in the present work; all the clays contained TiO2 and Fe2O3, but Clay12 had the highest content of both oxides. Table 1 also shows the presence of other oxides, such as MgO, P2O4, K2O, CaO, MnO, Co3O4, SnO2, and CeO2. It was clear that the CB edge of TiO 2 was more negative than the CB edge of ZnTiO 3 ; on the other hand, the VB edge of ZnTiO 3 was more positive than the VB edge of TiO 2 . Consequently, the electrons excited from the CB of TiO 2 jumped to the CB of ZnTiO 3 , and the holes generated from the VB of ZnTiO 3 transferred to the VB of TiO 2 , which caused an efficient separation of e − and h + , and the photocatalytic activity improved due to the ZnTiO 3 /TiO 2 heterojunction [27,44,45].

XRF Analysis
Clays are minerals that are widely distributed in nature, being produced by the erosion of rocks. The texture and chemical composition of the clays are greatly varied, depending on the presence of organic and inorganic impurities as well as the geological origin of the clays. Table 1 shows the composition of the clays used in the present work; all the clays contained TiO 2 and Fe 2 O 3 , but Clay 12 had the highest content of both oxides.

Adsorption and Photocatalytic Degradation
Photocatalysts can degrade organics compounds due to strong oxidizing capacity they exhibit, especially when they are irradiated by light. In this work, the photocatalytic activity of the TiO 2 and ZnTiO 3 /TiO 2 photocatalyst was first tested by the degradation of methylene blue (MB) in water, using irradiation with both a) solar light and b) UV-C light. Figure 7 shows the results obtained in the test.

Adsorption and Photocatalytic Degradation
Photocatalysts can degrade organics compounds due to strong oxidizing capacity they exhibit, especially when they are irradiated by light. In this work, the photocatalytic activity of the TiO2 and ZnTiO3/TiO2 photocatalyst was first tested by the degradation of methylene blue (MB) in water, using irradiation with both a) solar light and b) UV-C light. Figure 7 shows the results obtained in the test.  Figure 7 shows that the highest removal percentage was obtained with UV-C irradiation; therefore, it was used for photocatalytic degradation tests with photocatalysts supported on clays. Figure 8 shows the photocatalytic activity of the clays and the clay supported photocatalyst. In all tests, the clays improve their catalytic activity with the presence of photocatalysts. ZnTiO3/TiO2 have higher photocatalytic activity than TiO2 in almost all the clays. In this Figure, it is observed that Clay12 and the photocatalyst-Clay12 composites had the highest photocatalytic activity.   Figure 7 shows that the highest removal percentage was obtained with UV-C irradiation; therefore, it was used for photocatalytic degradation tests with photocatalysts supported on clays. Figure 8 shows the photocatalytic activity of the clays and the clay supported photocatalyst. In all tests, the clays improve their catalytic activity with the presence of photocatalysts. ZnTiO 3 /TiO 2 have higher photocatalytic activity than TiO 2 in almost all the clays. In this Figure, it is observed that Clay 12 and the photocatalyst-Clay 12 composites had the highest photocatalytic activity.
Photocatalysts can degrade organics compounds due to strong oxidizing capacity they exhibit, especially when they are irradiated by light. In this work, the photocatalytic activity of the TiO2 and ZnTiO3/TiO2 photocatalyst was first tested by the degradation of methylene blue (MB) in water, using irradiation with both a) solar light and b) UV-C light. Figure 7 shows the results obtained in the test.  Figure 7 shows that the highest removal percentage was obtained with UV-C irradiation; therefore, it was used for photocatalytic degradation tests with photocatalysts supported on clays. Figure 8 shows the photocatalytic activity of the clays and the clay supported photocatalyst. In all tests, the clays improve their catalytic activity with the presence of photocatalysts. ZnTiO3/TiO2 have higher photocatalytic activity than TiO2 in almost all the clays. In this Figure, it is observed that Clay12 and the photocatalyst-Clay12 composites had the highest photocatalytic activity.   The surface morphology of Clay 12 and of the composites (TiO 2 -Clay 12 and ZnTiO 3 /TiO 2 -Clay 12 ) was investigated by SEM, and the results are shown in Figure 10, from which it can be seen that Clay 12 has a different surface morphology than composites of photocatalyst-Clay 12 . The surface morphology of Clay 12 seems as a smooth surface in some parts of the particle, while the composites of photocatalyst-Clay 12 , has some catalysts particles incorporated into its surface (smaller TiO 2 and ZnTiO 3 /TiO 2 grains on the outer face of Clay 12 ). The EDX spectra confirms that the composites contain an important amount of titanium and zinc, as shown in Figure 10.  The surface morphology of Clay12 and of the composites (TiO2-Clay12 and ZnTiO3/TiO2-Clay12) was investigated by SEM, and the results are shown in Figure 10, from which it can be seen that Clay12 has a different surface morphology than composites of photocatalyst-Clay12. The surface morphology of Clay12 seems as a smooth surface in some parts of the particle, while the composites of photocatalyst-Clay12, has some catalysts particles incorporated into its surface (smaller TiO2 and ZnTiO3/TiO2 grains on the outer face of Clay12). The EDX spectra confirms that the composites contain an important amount of titanium and zinc, as shown in Figure 10.   The surface morphology of Clay12 and of the composites (TiO2-Clay12 and ZnTiO3/TiO2-Clay12) was investigated by SEM, and the results are shown in Figure 10, from which it can be seen that Clay12 has a different surface morphology than composites of photocatalyst-Clay12. The surface morphology of Clay12 seems as a smooth surface in some parts of the particle, while the composites of photocatalyst-Clay12, has some catalysts particles incorporated into its surface (smaller TiO2 and ZnTiO3/TiO2 grains on the outer face of Clay12). The EDX spectra confirms that the composites contain an important amount of titanium and zinc, as shown in Figure 10.  Figure 11 shows the adsorption results of the clays and clay-supported photocatalysts. Most clays exceed the adsorption capacity of clay-supported photocatalysts. However, TiO2 improves the adsorption capacity of Clay5 while ZnTiO3 slightly improves the adsorption capacity of Clay7, Clay11, and Clay12. In Clay1, the presence of photocatalysts did not affect the adsorption capacity of the clay.  Figure 11 shows the adsorption results of the clays and clay-supported photocatalysts. Most clays exceed the adsorption capacity of clay-supported photocatalysts. However, TiO 2 improves the adsorption capacity of Clay 5 while ZnTiO 3 slightly improves the adsorption capacity of Clay 7 , Clay 11 , and Clay 12 . In Clay 1 , the presence of photocatalysts did not affect the adsorption capacity of the clay.
. (c) Figure 10. SEM image and EDX spectra of: (a) Clay12; (b) TiO2-Clay12; (c) ZnTiO3/TiO2-Clay12. Figure 11 shows the adsorption results of the clays and clay-supported photocatalysts. Most clays exceed the adsorption capacity of clay-supported photocatalysts. However, TiO2 improves the adsorption capacity of Clay5 while ZnTiO3 slightly improves the adsorption capacity of Clay7, Clay11, and Clay12. In Clay1, the presence of photocatalysts did not affect the adsorption capacity of the clay. In Figure 11, Clay6 shows the highest MB removal capacity. The XRD pattern in Figure 12 shows that Clay6 consists mainly of Metahalloysite (M) and Quartz (Q), which could also contribute to the high adsorption capacity of the clay. This clay has a specific surface area of 42.8 m 2 /g, which was Figure 11. Adsorption capacity of MB for clay and clay-supported photocatalysts.
In Figure 11, Clay 6 shows the highest MB removal capacity. The XRD pattern in Figure 12 shows that Clay 6 consists mainly of Metahalloysite (M) and Quartz (Q), which could also contribute to the high adsorption capacity of the clay. This clay has a specific surface area of 42.8 m 2 /g, which was calculated from N 2 gas adsorption using the Brunauer-Emmet-Teller (BET) isotherm in the Chemisorb 2720 equipment coupled to TPx.   Figure 13 show the surface morphology of Clay6 and of the composites (TiO2-Clay6 and ZnTiO3/TiO2-Clay6) examined by SEM. From this Figure, it can be seen that Clay6 has a different surface morphology than composites of photocatalyst-Clay6. The surface morphology of Clay6 seems to be a flake-like structure, while in the composites of photocatalyst-Clay6, the surface appears with less flake but with some catalyst particles incorporated (smaller TiO2 and ZnTiO3/TiO2 grains) on the outer face of Clay6. The changes in the morphology of Clay6 is due to the thermal treatment to incorporate the photocatalysts. This treatment decreased the specific surface area of Clay6 to 27.2 m 2 /g and 25.8 m 2 /g when impregnated with TiO2 and ZnTiO3, respectively. The EDX spectra confirms that  Figure 13 show the surface morphology of Clay 6 and of the composites (TiO 2 -Clay 6 and ZnTiO 3 /TiO 2 -Clay 6 ) examined by SEM. From this Figure, it can be seen that Clay 6 has a different surface morphology than composites of photocatalyst-Clay 6 . The surface morphology of Clay 6 seems to be a flake-like structure, while in the composites of photocatalyst-Clay 6 , the surface appears with less flake but with some catalyst particles incorporated (smaller TiO 2 and ZnTiO 3 /TiO 2 grains) on the outer face of Clay 6 . The changes in the morphology of Clay 6 is due to the thermal treatment to incorporate the photocatalysts. This treatment decreased the specific surface area of Clay 6 to 27.2 m 2 /g and 25.8 m 2 /g when impregnated with TiO 2 and ZnTiO 3 , respectively. The EDX spectra confirms that the composites contain an important amount of titanium and zinc, as shown in Figure 13.  Figure 13 show the surface morphology of Clay6 and of the composites (TiO2-Clay6 and ZnTiO3/TiO2-Clay6) examined by SEM. From this Figure, it can be seen that Clay6 has a different surface morphology than composites of photocatalyst-Clay6. The surface morphology of Clay6 seems to be a flake-like structure, while in the composites of photocatalyst-Clay6, the surface appears with less flake but with some catalyst particles incorporated (smaller TiO2 and ZnTiO3/TiO2 grains) on the outer face of Clay6. The changes in the morphology of Clay6 is due to the thermal treatment to incorporate the photocatalysts. This treatment decreased the specific surface area of Clay6 to 27.2 m 2 /g and 25.8 m 2 /g when impregnated with TiO2 and ZnTiO3, respectively. The EDX spectra confirms that the composites contain an important amount of titanium and zinc, as shown in Figure 13.

Reuse of the Supported Photocatalysts
The recyclability and stability of the photocatalysts are important factors for their application in large scale; therefore, five consecutive photocatalytic experiments were carried out for the extrudates of Clay6, photocatalyst-Clay6, Clay12, and photocatalyst-Clay12. Figure 14 shows the degradation efficiency of these materials for five cycles.

Reuse of the Supported Photocatalysts
The recyclability and stability of the photocatalysts are important factors for their application in large scale; therefore, five consecutive photocatalytic experiments were carried out for the extrudates of Clay 6 , photocatalyst-Clay 6 , Clay 12 , and photocatalyst-Clay 12 . Figure 14 shows the degradation efficiency of these materials for five cycles.

Reuse of the Supported Photocatalysts
The recyclability and stability of the photocatalysts are important factors for their application in large scale; therefore, five consecutive photocatalytic experiments were carried out for the extrudates of Clay6, photocatalyst-Clay6, Clay12, and photocatalyst-Clay12. Figure 14 shows the degradation efficiency of these materials for five cycles.   Figure 14 clearly shows that the percentage of MB removal decreases slightly with increasing cycle times. However, after five cycles, the synthesized materials still have high activity and can efficiently degrade MB in aqueous solution.

Synthesis and Characterization of the TiO 2 /ZnTiO 3 -Clay Composite
In this work, ZnTiO 3 /TiO 2 nanoparticles were successfully synthesized using the sol-gel method and supported on twelve raw clays of Ecuadorian origin. In the synthesis process when the TiO 2 /ZnO molar ratio was decreased, the formation of TiO 2 also decreased, but the formation of ZnTiO 3 increased due to the greater availability to form the heterostructure. The obtained nanomaterial of ZnTiO 3 /TiO 2 heterostructure had high purity and no other crystalline phases were observed for the sample. This results are consistent with those reported by Bhagwat et al., who synthesized ZnTiO 3 @TiO 2 at 700 • C using TiO 2 (P-25) with zinc nitrate as a precursor [28].
Several calcination temperatures were tested for the synthesis of the ZnTiO 3 /TiO 2 heterostructure. When the heat treatment temperature was increased to 500 • C, TiO 2−a (anatase phase) was the primary crystalline phase with TiO 2-r (rutile phase) traces. In addition, a hexagonal phase of ZnTiO 3 was also present in the sample prepared at 500 • C. With a temperature increment from 600 • C to 900 • C, TiO 2−r appeared, and TiO 2−a disappeared completely. However, the hexagonal phase of ZnTiO 3 still existed in the sample at 900 • C. This indicates that TiO 2−r was transformed from TiO 2−a , but not by decomposition of ZnTiO 3 . This is in agreement with previous studies which revealed that the phase transition from TiO 2−a to TiO 2−r occur in a temperature range of 600-1100 • C [41]. In addition, the hexagonal ZnTiO 3 would decompose at about 1000 • C into the metastable form Zn 2 Ti 3 O 8 and finally to the stable cubic phase Zn 2 TiO 4 with TiO 2−r . These results agree with the conclusions of several authors, who indicate the presence of a low percentage of zinc oxide formation from the metastable ZnTiO 3 which ultimately transforms (>90% conversion) to Zn 2 TiO 4 (<900 • C) and to TiO 2−r from 700 • C [38,[42][43][44]. The literature also indicates that obtaining either of these Ti-Zn mixed oxides as phase-pure at a low processing temperature is a challenge in materials chemistry [26,38]. On the other hand, SEM images were used to determine the shape, particle size, and morphology of the samples. The ZnTiO 3 /TiO 2 heterostructure synthesized with a TiO 2 :ZnO molar ratio of 3:1 and calcined at 500 • C was almost spherical with an average particle size of 100 nm and, highly agglomerated. These results agree with those reported by Mehrabi et al. [42].
According to Equation (2), the calculated band gaps of ZnTiO 3 /TiO 2 and TiO 2 for the present study were 3.07 and 3.12 eV, respectively. These values are smaller than those reported by Li et al. [45], who synthesized a-TiO 2 /ZnTiO 3 and a-TiO 2 nanoparticles with a particle size smaller than 100 nm and found band gap values of 3.14 and 3.23 eV for both photocatalysts, respectively. This band gap difference may be due to the difference in particle size also known as the quantum size effect [39]. To improve conversion efficiency, a good alternative is to reduce the band gap to shift the spectral range of light absorption into the visible-light region and even the near-infrared light region [46]. Therefore, the ZnTiO 3 /TiO 2 composite synthesized in the present study could be a promising alternative for the photocatalytic degradation of colorants in aqueous systems due to its band gap.

Adsorption and Photocatalytic Degradation
The photocatalytic activity of the clay-supported ZnTiO 3 /TiO 2 was determined by decomposition under UV-C light irradiation of Methylene Blue (MB) in water following the methodology described by Ke et al. [41], with some modifications. The literature reports that UV light excites photocatalysts to decompose the organic pollutant due to the generation of electron pairs and VB holes (e − /h + ) produced. The e − and h + can move in the catalyst. When they move to the surface of the catalyst, e − reacts with O 2 in the solution to generate *OH and *O 2 radicals. These active species then react with MB to oxidize it and transform it into small molecules, thus achieving both purposes, decolorization and degradation of the organic matter [31,[46][47][48].
The results obtained in the present study clearly indicate that ZnTiO 3 /TiO 2 possesses excellent photocatalytic performance. These results are in line with the findings of several authors [49][50][51][52][53]. Furthermore, the ZnTiO 3 /TiO 2 composite exhibited an important increase of the photocatalytic activity as compared with pure TiO 2 . The composite probably had better photocatalytic activity because the coupling promotes an effective separation of photo-generated electron-hole pairs between TiO 2 and ZnTiO 3 [41].
Ke et al. [41] reported the photocatalytic activity of a-TiO 2 , a-TiO 2 /ZnTiO 3, and r-TiO 2 /ZnTiO 3 . These authors synthesized a-TiO 2 /ZnTiO 3 at 800 • C and found that it had the highest photocatalytic activity, removing approximately 80% of the dye from a 5 mg/L MB solution and under UV-C light. In the present study, ZnTiO 3 /TiO 2−a was synthesized at 500 • C and approximately 90% of the dye was removed from an MB solution of the same concentration and under UV-C light. This improvement is probably due to the TiO 2 :ZnO molar ratio used in the present study, which may improve the separation of the electron-hole pairs [41].
On the other hand, in agreement with other authors [54][55][56][57][58][59][60][61], the clay minerals and clay-derived materials have many diverse applications including catalysis and adsorption, which are based on their unique surface properties. The evidence of this work indicates that raw clays can be valuable supports for materials used for the removal of dyes.
The high photocatalytic activity of Clay 12 and its photocatalytic derivatives is probably caused by the presence of natural TiO 2 in its composition. This clay shows also a deep-red color due to the presence of a high content of Fe 2 O 3 . The photocatalytic derivatives of TiO 2 and both Clay 1 and Clay 2 also show high photocatalytic activity, probably due to their mineralogical composition. Both clays are rich in SiO 2 , and according to the literature, TiO 2 /SiO 2 photocatalysts exhibit high photocatalytic activity toward pollutant molecule decomposition [62].
In the present study, Clay 6 shows the highest MB removal capacity. According to the literature, electrostatic interaction, complexation chemical reactions, or ionic exchange between the adsorbent and the adsorbate are some of the mechanisms that may be involved in the adsorption of MB on the surface of clay minerals [2,59]. Clay 6 has a zero-charge point (ZCP) of 3.0. The ZCP of both TiO 2 and ZnTiO 3 /TiO 2 supported in Clay 6 was 7.0. The tests were carried out at pH = 8.0; therefore, the surface of Clay 6 was negatively charged, improving the MB cation adsorption. Moreover, according to Table 1, Clay 6 presents several oxides, such as MgO, K 2 O, CaO, TiO 2 , MnO, and others that could promote the cationic exchange capacity of the clay to improve its adsorption capacity [63,64]. Furthermore, Clay 6 contains Metahalloysite (M), which could also contribute to the high adsorption capacity of the clay since, according to the literature, metahalloysite has a potential application in the design and preparation of heterogeneous catalysts in procedures where the temperature did not exceed 450 • C [65].
It is important to mention that prior to illumination, MB was adsorbed onto the composites surface for 30 min in the dark and the average adsorption capacity was of 73%, 66%, 63%, 55%, and 46% approximately for Clayx, ZnTiO 3 /TiO 2 -Clayx, TiO 2 -Clayx, ZnTiO 3 /TiO 2, and TiO 2 , respectively. It is evident from these results that adsorption played a significant role in the degradation process of MB but is not sufficient to achieve complete degradation. Batch adsorption was therefore followed by 150 min of photocatalysis to further improve the degradation process. After 150 min of illumination, the average decolorization was improved to 89%, 82%, 85%, 92%, and 89% approximately for Clayx, ZnTiO 3 /TiO 2 -Clayx, TiO 2 -Clayx, ZnTiO 3 /TiO 2, and TiO 2 , respectively, which confirmed that adsorption combined with photocatalysis is an efficient process for dye degradation. These results agree with those obtained by other authors for the degradation of MB by adsorption and photocatalysis [66][67][68][69][70][71].
It is known that the separation, recovery, and reuse of the photocatalyst particles are important issues determining the future application of photocatalytic technology [72]. Therefore, in the present work, extrudates of photocatalyst-clay were prepared to facilitate the recovery of the synthesized composites. The extrudates preserved their structure during the process and no fine particles from attrition were observed; however, filters were used prior to spectrophotometer determination to avoid any interference. The use of clay extrudates with immobilized nanostructured semiconductors was an effective alternative to obtain porous photocatalysts with better active surface and adsorption capacity than isolated semiconductors, preserving their electronic and structural properties for their application in the degradation of MB under UV-C irradiation.

Reuse of the Supported Photocatalysts
Mechanical stability is an especially important property, which is directly related to the useful life of the supported photocatalyst. When the mechanical stability is poor, the photocatalyst will gradually flake away from the support into the reaction solution during the process; consequently, the supported photocatalyst loses its activity prematurely, and causes both secondary contamination and waste of the photocatalyst. Some investigations results showed that mechanical stability of the material is correlated with the calcination temperature [73]. Consequently, increasing the calcination temperature produces better mechanical stability, although there is an optimal calcination temperature to achieve maximum mechanical stability. In the present work, a maximum calcination temperature of the extrudates of 500 • C was used to avoid the change of crystalline phase of the synthesized photocatalysts. On average, the loss of activity of the materials did not exceed 10% at the end of the fifth cycle; thus, 500 • C is the optimum calcination temperature to achieve adequate photocatalytic activity and reuse property under the operating conditions used in this study.
Finally, the synthesized clay-supported composite reported in this paper could be an efficient alternative to remove dyes in aqueous effluents and the most probable reason is the combined effects of several factors, such as the specific surface area, the crystal size and crystallization phases, absorption capacity, photocatalytic activity, and mechanical stability. Table 2 shows the comparison of the MB degradation capacity of the main synthesized composites with other composites reported in the literature.

Conclusions
In summary, according to the results obtained, it can be concluded that the sol-gel method is useful to synthesize other perovskite-type oxides based on titanium with various architectures and novel properties. Different operating conditions were evaluated to determine the best TiO 2 /ZnO molar ratio and the optimum synthesis temperature to obtain ZnTiO 3 /TiO 2 . The results indicate that the best synthesis conditions were the following: a molar ratio of 3:1 and a calcination temperature of 500 • C. The photocatalytic materials were tested for the removal of methylene blue and, as a result, it was obtained that ZnTiO 3 /TiO 2 had better activity than TiO 2−a . Twelve Ecuadorian clays were characterized, some of them with exploitation potential and utility in the preparation of new materials. The photocatalysts were impregnated into the clays and their photocatalytic activity and adsorption capacity were evaluated. Clay 12 impregnated with TiO 2−a showed the best photocatalytic activity. The X-ray fluorescence results showed that Clay 12 has TiO 2 and Fe 2 O 3 in its composition, which could improve its activity. Clay 6 had the best methylene blue adsorption capacity. The results of the X-ray diffraction allowed concluding that the presence of metahalloysite phase improves the adsorption capacity. In addition, Clay 6 has various oxides with exchange cations that could improve its adsorption capacity. Thus, both clays can be used as inexpensive materials for the removal of cationic dyes from wastewater. Nevertheless, the adsorption mechanisms and adsorption reversibility should be further investigated to confirm the efficiency of these clays, as well as to elucidate which are the adequate active sites to prevent the release of cationic dyes depending on the physical-chemical conditions.