Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> hollow spheres and their activity in methylene blue photodecomposition

PSA [poly-(styrene-methyl acrylic acid)] latex particle has been taken into account as template material in SiO₂ hollow spheres preparation. TiO₂-doped SiO₂ hollow spheres were obtained by using the appropriate amount of Ti(SO₄)₂ solution on SiO₂ hollow spheres. The photodecomposition of the MB (methylene blue) was evaluated on these TiO₂-doped SiO₂ hollow spheres under UV light irradiation. The catalyst samples were characterized by XRD, UV-DRS, SEM and BET. A TiO₂-doped SiO₂ hollow sphere has shown higher surface area in comparison with pure TiO₂ hollow spheres. The 40 wt% TiO₂-doped SiO₂ hollow sphere has been found as the most active catalyst compared with the others in the process of photodecomposition of MB (methylene blue). The BET surface area of this sample was found to be 377.6 m²g⁻¹. The photodegradation rate of MB using the TiO₂-doped SiO₂ catalyst was much higher than that of pure TiO₂ hollow spheres.     

Hydrophilicity and crystallization behavior of PVDF/PMMA/TiO<Subscript>2</Subscript>(SiO<Subscript>2</Subscript>) composites prepared by in situ polymerization

Composites with enhanced hydrophilicity were prepared by adding TiO₂ or SiO₂ nanoparticles during the in situ polymerization of methyl methacrylate (MMA) in poly(vinylidene fluoride) (PVDF). The hydrophilicities of the PVDF/PMMA/TiO₂(SiO₂) composites generated in this manner were characterized by contact angle measurements and atomic force microscopy (AFM). The hydrophilicity was dependent on nanoparticle content; it gradually increased with increasing TiO₂ (or SiO₂) content when the TiO₂ (or SiO₂) content was no more than 4 wt% of PVDF. A homogeneous dispersion of the TiO₂ (or SiO₂) nanoparticles in the composite matrix was observed in scanning electron microscope (SEM) images. Based on Fourier transform infrared (FTIR) spectra and wide angle X-ray diffraction (WAXD) analyses, the crystalline phase composition of PVDF was not influenced by the addition of TiO₂ (or SiO₂); PVDF crystallized predominantly in the α phase after in situ polymerization. Nevertheless, the nanoparticles can promote the formation of the β phase of PVDF in composites; the β-phase content increased with increasing TiO₂ content, while it was almost independent of SiO₂ content.     

Solid acidities of SiO2–TiO2/montmorillonite composites synthesized under different pH conditions

SiO₂–TiO₂/montmorillonite composites were prepared under acidic, neutral and basic conditions and the solid acidity of the resulting composites were determined. All the SiO₂/TiO₂ ratio of the colloidal particles was set at 10 but the resulting SiO₂/TiO₂ ratios were significantly richer in TiO₂. The XRD patterns of the acidic composite showed expanding and broadening of the (001) reflection by intercalation of colloidal SiO₂–TiO₂ particles, but the neutral and basic composites showed only broadening of the reflections and no intercalation. The specific surface areas of the acidic, neutral and basic composites (375, 237 and 247 m²/g, respectively) were much larger than of montmorillonite (6 m²/g). The average pore sizes were about 4, 15 and 50 nm, and the amounts of solid acidic sites measured by the NH₃-TPD were 178, 95 and 86 µmol/g for the acidic, neutral and basic composites, respectively. The solid acid amount of the acidic composite was twice that of a commercial catalyst, K-10, (85 µmol/g) and much higher than the guest phase SiO₂–TiO₂ gel (16 µmol/g) or the host phase montmorillonite (6 µmol/g). The TPD peak temperatures reflect the acid strength, and were similar in all the samples, ranging from 175° to 200 °C.     

Characterizations of TiO2/SiO2/Ni–Cu–Zn Ferrite Composite for Magnetic Photocatalysts

The TiO₂/SiO₂/Ni–Cu–Zn ferrite composite for magnetic photocatalysts with high photocatalytic activity is successfully prepared in this study. The composite are composed of spherical or elliptical Ni–Cu–Zn ferrite nanoparticles about 20–60 nm as magnetic cores, silica as barrier layers with thickness of 15 nm between the magnetic cores and titania shells with thickness approximately 1.5 nm. Photodegradation examination of TiO₂/SiO₂/ Ni–Cu–Zn ferrite composite was carried out in methylene blue (MB) solutions illuminated under a Xe arc lamp with 35 W and color temperature of 6000 K. The results indicated that about 47.1% of MB molecules adsorbed on the TiO₂/SiO₂/Ni–Cu–Zn ferrite composite within 30 min mixing due to it higher pore volume of 0.034 cm³/g, and after 6 h Xe lamp irradiation, 83.9% of MB 16.1% was photodegraded. Compared with the TiO₂ /Ni–Cu–Zn ferrite composite, the TiO₂/SiO₂/Ni–Cu–Zn ferrite composite with silica barrier layer prohibited the photodissolution and enhanced the photocatalytic ability. The magnetic photocatalyst shows high photocatalytic efficiency that the apparent first‐order rate constant k_obs is 0.18427 h^?1, and good magnetic property that the saturation magnetization (M_s) of is 37.45 emu/g, suggesting the magnetic photocatalyst can be easily recovered by the application of an external magnetic field.     

Radiation Synthesis and Characterization of Poly (vinyl alcohol)/acrylamide/TiO2/SiO2 Nanocomposite for Removal of Metal Ion and Dye from Wastewater

PVA-co-AAm/TiO₂/SiO₂ nanocomposites adsorbents synthesized by γ-irradiation copolymerization of polyvinyl alcohol (PVA) and acrylamide (AAm) incorporated TiO₂/SiO₂ nanopowders, aiming to enhance the removal of basic blue 3 dye (BB3) and Cu (II) ions from aqueous solutions. Properties of nanocomposites were analyzed by different techniques. FTIR results showed successful incorporation of nanoparticles and copolymerization of PVA and AAM. SEM/EDS confirm the peaks belonging to C, O, Si, and Ti. TEM investigation illustrated that TiO₂/SiO₂ nanoparticles were well dispersion, uniform, and homogeneous shape of particle size of 60–70 nm. XRD data specified characteristic diffraction peaks of TiO₂ and the calculated crystalline size was 43 nm. Adsorption results confirm that PVA-co-AAm/TiO₂/SiO₂ nanocomposites provide better adsorption capacities of both BB3 and Cu (II) was three-folds rather than PVA-co-AAm-30. The nanocomposite prepared at 30 kGy (PVA-co-AAm/TiO₂/SiO₂-30) showed high swelling, gelation, and highest adsorption capacity and it was selected as the best adsorbent for batch experiments. The optimum adsorption was achieved using 0.4 g PVA-co-AAm/TiO₂/SiO₂-30 adsorbent dosage. The adsorption capacity of BB3 and Cu (II) was 140.9 and 190.3 mg/g with a removal efficiency of 93.5 and 95.2% after 7 h and 6 h, pH 11 and pH 6, and initial concentration of 150 and 200 mg/L, respectively. The adsorption of BB3 or Cu (II) was endothermic and spontaneous, well described by the pseudo-second-order adsorption kinetic and fit Langmuir isotherm. The results revealed that the as-synthesized PVA-co-AAm/TiO₂/SiO₂ nanocomposites could be employed as effective adsorbents for the adsorption of BB3 and Cu (II) ions from wastewater with high adsorption capacity and recovery.

     

Electrochemical preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite film and its high activity toward the photoelectrocatalytic degradation of methyl orange

Uniform TiO₂/SiO₂ composite films were prepared on ITO substrates by electrodeposition, and highly photoelectrocatalytic (PEC) activity of the composite films was observed toward the degradation of methyl orange (MO) in aqueous solutions. It was further found that their PEC activity was dependent on the electrodeposition parameters including deposition time, solution pH and SiO₂ content. Under the optimized condition, the PEC degradation of MO on TiO₂/SiO₂ composite film electrode could be enhanced about 14 times relative to that on neat TiO₂ film electrode. The high PEC activity of the TiO₂/SiO₂ composite film electrode was mainly attributed to the enhancement of the charge separation of photo-generated electron-hole pairs by the dispersion of SiO₂ nanoparticles in the TiO₂ matrix with the aid of the applied electric field.     

Fabrication of superhydrophilic self-cleaning SiO2–TiO2 coating and its photocatalytic performance

Generally, superhydrophilic self-cleaning coatings are prepared from semiconductors with photocatalytic properties. Organic pollutants attached to the coating surface can be degraded by its photocatalytic performance realizing a self-cleaning goal. Herein, SiO₂–TiO₂ composite particles were fabricated by the hydrolysis and precipitation of TiOSO₄, and SiO₂ microspheres were chosen as carriers, which are inexpensive and environmentally friendly. Then, superhydrophilic self-cleaning SiO₂–TiO₂ coatings were fabricated by spraying the composites on the surfaces of substrates. The morphology, structure and self-cleaning performance of the SiO₂–TiO₂ coating were characterized and tested. The results revealed that nano-TiO₂ was loaded on the surfaces of SiO₂ microspheres uniformly forming a hierarchical micro/nanostructure. The SiO₂–TiO₂ composite particles exhibited excellent photocatalytic degradation performance, and the degradation rate of methyl orange (10 ppm) was more than 98% under UV irradiation for 40 min. Furthermore, the coating prepared with the SiO₂–TiO₂ composite particles exhibited superhydrophilicity. A water droplet spreads completely on the coating surface in 0.35 s, and the contact angle reaches 0°. In addition, rhodamine B (RhB) and methylene blue (MB) on the coating surface can be degraded efficiently under sunlight irradiation. The SiO₂–TiO₂ composite particles can be sprayed directly on the surfaces of concrete, brick, wood, and glass slides. Therefore, the particles showed good adaptability to different substrates. The superhydrophilic property was due to the hydrophilicity of SiO₂ and TiO₂, the hierarchical micro/nanostructure of the SiO₂–TiO₂ composites, and the photoinduced superhydrophilicity of TiO₂. The above experimental results show that the as-prepared superhydrophilic self-cleaning SiO₂–TiO₂ coating has a large application potential.     

Synthesis of TiO<Subscript>2</Subscript> Nanoparticles by Microemulsion/Heat Treated Method and Photodegradation of Methylene Blue

In this work, TiO₂ nanoparticles were prepared by microemulsion (ME)/heat treated method and its photodecomposition property of methylene blue. Microemulsion (ME) consisted of water, cyclohexane and an anionic surfactant such as bis (2-ethylhexyl) sodium sulfosuccinate (AOT). Titanium tetraisopropoxide (TTIP) was dropped into the ME solution and then then TiO₂ nanoparticles were formed by the hydrolysis reaction between TTIP in the organic solvent and the water in the core of ME. The smallest diameter of the particles was 20 nm in the system of cyclohexane with surfactant when the molar ratio of water to surfactant was 2. The effect of the process parameters (water/surfactant ratio, different temperatures) on the final characteristics has been investigated, in terms of structural phase and particle size. The TiO₂ nanoparticles were characterized by means of X-ray diffraction, Transmission and scanning electron microscopy, Fourier-Transformed infrared and differential thermal analysis. TiO₂ nanoparticles prepared in this condition were collected as amorphous powder, and converted to anatase phase at less than 350 °C, which is lower than the ordinal phase transition temperature. The crystallite size and crystallinity increase with an increase of heat treated s temperature. The particles are shown to have a spherical shape and have a uniform size distribution. The size of nanoparticles raises with an increase of water/surfactant ratio. In the photocatalytic decomposition of methylene blue, the photocatalytic activity is mainly determined by the crystallinity of TiO₂. In addition, the TiO₂ heat treated at 350 °C shows the highest activity on the photocatalytic decomposition of methylene blue (k = 1.7 × 10⁻² min⁻¹).     

Preparation of hydrophobic SiO<Subscript>2</Subscript>@(TiO<Subscript>2</Subscript>/MoS<Subscript>2</Subscript>) composite film and its self-cleaning properties

TiO₂/MoS₂ composite was encapsulated by hydrophobic SiO₂ nanoparticles using a sol–gel hydrothermal method with methyltriethoxysilane (MTES), titanium tetrachloride (TiCl₄), and molybdenum disulfide (MoS₂) as raw materials. Then, a novel dual functional composite film with hydrophobicity and photocatalytic activity was fabricated on a glass substrates via the combination of polydimethylsiloxane adhesives and hydrophobic SiO₂@(TiO₂/MoS₂) composite particles. The influence of the mole ratios of MTES to TiO₂/MoS₂ (M:T) on the wettability and photocatalytic activity of the composite film was discussed. The surface morphology, chemical compositions, and hydrophobicity of the composite film on the glass substrate were investigated by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and water contact angle (water CA) measurements. The results indicated that the composite film exhibited stable superhydrophobicity and excellent photocatalytic activity for degradation of methyl orange (MO) even after five continuous cycles of photocatalytic reaction when M/T was 7:1. The water CA and degradation efficiency for MO remained at 154° and 94%, respectively. Further, the composite film showed a good non-sticking characteristic with the water sliding angle (SA) at about 4°. The SiO₂@(TiO₂/MoS₂) composite consisting of hydrophobic SiO₂ nanoparticles and TiO₂/MoS₂ heterostructure could provide synergistic effects for maintaining long-term self-cleaning performance.     

Effect of Carbon Nanotubes and Carbon Nanotubes/Gold Nanoparticles Composite on the Photocatalytic Activity of TiO2 and TiO2‐SiO2

A carbon nanotube (CNT)/gold nanoparticle (NP) nanocomposite was synthesized by simultaneously reducing the Au ions and depositing Au NPs on the surface of a CNT. The functional groups were investigated with Fourier transform infrared spectra. From the Raman spectra, the D‐band and G‐band of the CNT were identified. The deposition of nanometer‐sized Au NPs on the CNT sites was observed by transmission electron microscopy. The photodegradation of methylene blue (MB) in aqueous solutions was studied using various photocatalysts, including TiO₂, TiO₂‐SiO₂, CNT/TiO₂, CNT/TiO₂‐SiO₂, Au/TiO₂, CNT‐Au/TiO₂, and CNT‐Au/TiO₂‐SiO₂ composites. CNT addition leads to a synergic effect, improving the photoactivity of the catalysts. A possible physically based mechanism was proposed involving the reduction of electron‐hole recombination and fast electron‐transfer possibility.     

Direct Solvothermal Formation of Nanocrystalline TiO2 on Porous SiO2 Adsorbent and Photocatalytic Removal of Nitrogen Oxides in Air over TiO2–SiO2 Composites

Solvothermal decomposition of titanium(IV) tert-butoxide (TTB) in toluene at 573 K in the presence of silica gel (SiO₂) with continuous stirring yielded a titanium(IV) oxide (TiO₂)–SiO₂ composite in which agglomerates of nanocrystalline TiO₂ were deposited on the surfaces of SiO₂ particles. Various TiO₂–SiO₂ composites having different TiO₂ contents can be synthesized by changing the ratio of TTB and SiO₂, and the composites had large surface areas corresponding to porous properties of SiO₂. These TiO₂–SiO₂ composites were used for photocatalytic removal of nitrogen oxides in air and their photocatalytic performances were compared with those of other TiO₂–SiO₂ samples prepared by different methods. Solvothermally synthesized 74 wt.%TiO₂–SiO₂ composite exhibited excellent photocatalytic performance (almost stoichiometric removal of NO _x (98%) and very low NO₂ release (0.3%)) attributable to high photocatalytic activity of TiO₂ and high adsorption property of SiO₂. Lesser performance of 74 wt.%TiO₂–SiO₂ composites prepared by other methods suggested that pore-mouth plugging of SiO₂ by TiO₂ and lower level of mixing of TiO₂ and SiO₂ decreased photocatalytic performance of the composites.     

Photocatalytic activity of metal-decorated SiO<Subscript>2</Subscript>@TiO<Subscript>2</Subscript> hybrid photocatalysts under water splitting

We report the fabrication of a metal-decorated hybrid nanocomposite with TiO₂ encapsulation (Metal/SiO₂@TiO₂, Metal=Pt or Ru) using a simple surface-modification chemical process. Metal nanoparticles capped with polyvinylpyrrolidone were successfully assembled on functionalized SiO₂ via electrostatic interactions, after which a thin layer of TiO₂ was coated on the surface by the sol-gel process to avoid agglomeration of the coated silica spheres. Transmission electron microscopy studies confirmed that the metal nanoparticles were uniformly distributed throughout the surface of the SiO₂ with a thin layer of TiO₂. In addition, X-ray diffraction was employed to ensure the crystal structure of the uniformly coated thin TiO₂ layer. Even after calcination at 500 °C, the structure remained intact, confirming high thermal stability. The photocatalytic activity of the metal-decorated SiO₂/TiO₂ nanocomposites was evaluated using the H₂ evolution reaction. The Metal/SiO₂@TiO₂ catalysts show the photocatalytic water splitting efficiency for H₂ generation (i.e., 0.14% for Pt/SiO₂@TiO₂ and 0.12% for Ru/SiO₂@TiO₂), while there is no generation of H₂ on the Metal/SiO₂ without a coating layer. These results indicate that the anatase crystalline coating layer has good thermal and chemical stability and plays a significant role in photocatalytic H₂ production.     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite oxide and its photocatalytic degradation of rhodamine B

The composite semiconductor photocatalyst TiO₂/SiO₂ was prepared by template-hydrothermal method using carbon spheres as the template. The structural and optical properties of TiO₂/SiO₂ were characterized by XRD, SEM, BET, UV–Vis DRS, TG-DTA, PL techniques. The formation of hydroxyl radical on the surface of TiO₂/SiO₂ was studied with terephthalic acid as the probe molecule, combined with fluorescence technique. The results showed that the specific surface area of TiO₂/SiO₂ composite was 327.9 m²/g, and the specific surface area of TiO₂/SiO₂ was larger than that of pure TiO₂. Photocatalytic degradation of rhodamine B showed that TiO₂/SiO₂ composite oxide under visible light illumination 40 min, the degradation rate was 98.6 % and the degradation rate of pure TiO₂ was only 11.9 %. The apparent first-order rate constant of TiO₂/SiO₂ was 33 times that of pure TiO₂ and more than 6 times that of P25 when the molar ratio of Ti to Si was 1:1 under visible light irradiation. Moreover, it’s also as much as 5 times that of pure TiO₂ and is more than 1 times that of P25 under UV light irradiation 25 min. Based on the experimental results, ^·O₂ ^? and h⁺ were suggested to be the major active species which was responsible for the degradation reaction. The increased photocatalytic activity of TiO₂/SiO₂ may be mainly attributed to effectively suppressing the recombination of hole/electron pairs. After the photocatalyst TiO₂/SiO₂ was reused 5 times, the degradation rate of rhodamine B could reach 89.2 % under visible light irradiation. Moreover, The composite semiconductor photocatalyst TiO₂/SiO₂ was selective towards the degradation of rhodamine B.     

Impact of supercritical drying and heat treatment on physical properties of titania/silica aerogel monolithic and its applications

TiO₂–SiO₂ monolithic aerogels were homogeneously prepared using sol–gel method. Critical point of drying of TiO₂–SiO₂ gels with ethanol was studied for 30, 60, 90 and 120 min. Subsequently, the gels were dried with supercritical ethanol, resulting in amorphous aerogels that crystallized following heat treatment at 550 °C from 1 to 5 h. The TiO₂–SiO₂ aerogels were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and surface area measurements. The molar ratio of SiO₂:TiO₂ was 6 and the synthetic strategy revealed that TiO₂–SiO₂ aerogel, had a surface area 868 m²/g, particle size 40 nm, density 0.17 g/cm³ and 80% porosity. The finding indicated that from economic point of view, TiO₂–SiO₂ gel should be supercritical dried for 30 min and heat-treated for 5 h. The TiO₂–SiO₂ aerogel monoliths photocatalyst synthesized using sol–gel method provided insight into the characteristics that make a photocatalyst material well-suited for photodegradation of phenol and cyanide in an industrial waste stream containing Cl⁻, S²⁻ and NH₄⁺. Interestingly, after multiple reuse cycles (i.e. ≥7), photodegradation systems with regenerated photocatalyst showed a slightly decreasing of photoactivity 2–4%. The overall kinetics of photodegradation of either phenol or cyanide using TiO₂–SiO₂ aerogel photocatalyst was found to be of first order.     

Photocatalytic performance of Ru doped anatase mounted on silica for reduction of carbon dioxide

Ru doped anatase supported on silica was prepared by solid-state dispersion method and examined for the photocatalytic reduction of carbon dioxide in aqueous medium at ambient conditions. To assist in interpreting the photocatalytic behaviour of Ru-TiO₂/SiO₂, reference systems consisting of Ru doped TiO₂ and TiO₂ supported on SiO₂ were also analyzed and the conditions were optimized. Ru/TiO₂ photocatalysts with metal loadings of 0.1, 0.3, 0.5 and 1.0 wt% were prepared by impregnation method and a series of TiO₂/SiO₂ catalysts with low TiO₂ (1, 3, 5 and 10 wt%) contents were prepared by solid-state dispersion method. The photocatalysts were characterized using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), UV–vis DRS, FT-IR and Raman spectroscopy. The results showed that TiO₂ particles with Ru ions have higher photocatalytic activity than undoped TiO₂ and the optimum Ru loading was found to be 0.5 wt%. Nevertheless, the yield increased notably when TiO₂ was supported on SiO₂. This strong enhancement suggests that in 10 wt% TiO₂/SiO₂ the efficiency of charge separation is strongly influenced through the presence of TiOSi bridging bonds. On the contrary, Ru-TiO₂/SiO₂ has no significant improvement in activity over TiO₂/SiO₂ except that it shows nearly quadruple times higher activity for the formation of methanol than Ru/TiO₂. The difference in the photocatalytic activity is related to its physico-chemical properties.     

Preparation of graphene film decorated TiO2 nano-tube array photoelectrode and its enhanced visible light photocatalytic mechanism

Graphene film decorated TiO₂ nano-tube array (GF/TiO₂ NTA) photoelectrodes were prepared through anodization, followed by electrodeposition strategy. Morphologies and structures of the resulting GF/TiO₂ NTA samples were characterized by scanning electrons microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. In addition, the optical and photoelectrochemical properties were investigated through UV–visible light diffuse reflection spectroscopy, photocurrent response and Mott–Schottky analysis. Furthermore, the photodecomposition performances were investigated through yield of hydroxyl radicals and photocatalytic (PC) degradation of methyl blue (MB) under visible light irradiation. It was found that GF/TiO₂ NTA photoelectrode exhibited intense light absorption both in UV light and visible region, higher transient photoinduced current of 0.107 mA cm⁻² and charge carrier concentration of 0.84 × 10¹⁹ cm⁻³, as well as effective PC performance of 65.9% for the degradation of MB. Furthermore, contribution of several reactive species to the PC efficiency of GF/TiO₂ NTA photoelectrode was distinguished. Moreover, the enhanced visible light PC mechanism was proposed and confirmed in detail.     

Synthesis and characterization of a conducting polyaniline/TiO2−SiO2 composites

Polyaniline/TiO₂?SiO₂ composites were prepared by an in situ chemical oxidation polymerization approach in the presence of hybrid TiO₂?SiO₂ fillers. The obtained polyaniline/TiO₂?SiO₂ composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FTIR), X‐ray diffraction (XRD), thermogravimetry (TG), and current?voltage (I?V) measurements. SEM picture shows a variation in morphology of polyaniline (PANI) from fiber shape to relatively regular particle shape with increasing TiO₂?SiO₂ contents in the composites. The floccule‐like structures were observed by high resolution TEM, which may help improve the efficiency of conductive network. SEM, XRD, TG, and FTIR spectra all reveal that a relatively strong interaction exist between TiO₂?SiO₂ and PANI. The I?V characteristics in such composites indicate that the charge transport is mainly governed by the space charge effects, which occurs at the interface between the conducting PANI and TiO₂?SiO₂. Meanwhile, PANI/TiO₂?SiO₂ composites exhibit significant increase in conductivity than PANI/TiO₂ or PANI/SiO₂. The reasons about high conductivity of PANI/TiO₂?SiO₂ have also been discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2288–2295, 2013     

ZSM-5/TiO<Subscript>2</Subscript> Hybrid Photocatalysts: Influence of the Preparation Method and Synergistic Effect

In this work, the influence of the preparation method of ZSM-5/TiO₂ hybrids on the photocatalytic performance for removal of formaldehyde (HCHO) or trichloroethylene (C₂HCl₃) in gas phase was analyzed. For this purpose, two methods for the synthesis of the hybrids, the incipient wetness impregnation (I) and the mechanical mixing method (M), were selected. The photocatalysts were characterized by N₂ adsorption–desorption, TEM, UV–Vis spectroscopy, XRD and electrophoretic migration. Also, the adsorption ability of the individual materials and hybrids was analyzed. ZSM-5/TiO₂ hybrids showed higher photocatalytic activity than bare TiO₂, independently of the preparation method selected. Mechanical mixing is a simple and easily scalable method to prepare highly active photocatalyst with high amounts of titania. The internal diffusion processes of the reactants to the active sites could be improved due to the micro–mesoporous structure developed on these hybrids. Incipient wetness impregnation method leads to photocatalysts with higher photodegradation rates per active site. The hybrids synthetized by this method show TiO₂ nanoparticles homogeneously dispersed on the ZSM-5 phase. The fraction of TiO₂ exposed on the surface ca. 75 mol% was similar for materials prepared by both methods, explaining the similar adsorption and photocatalytic properties, independently of the TiO₂ content. The nature of the pollutant has an important role in the adsorption and photocatalytic properties of the composites. Finally, the effect of the incorporation of the zeolite in the photocatalytic system was analyzed. For this purpose, the influence of the zeolite and titania arrangement in the sample holder on the photodegradation rate was analyzed. Although the incorporation of the zeolite induces a positive effect on the photocatalytic performance, independently of the position on the sample holder, a clear synergistic effect when both phases were in intimate contact such as in the ZSM-5/TiO₂ hybrid was observed.     

Synthesis and characterization of mesoporous materials: Silica–zirconia and silica–titania

An experimental strategy was developed to obtain mesoporous SiO₂–ZrO₂ and SiO₂–TiO₂ mixed oxides by a sol–gel method, treating the gels hydrothermally. The solids were characterized by nitrogen physisorption, pyridine thermodesorption, ²⁹Si nuclear magnetic resonance, SEM and X-ray diffraction. The effects of ZrO₂ content, the generated pressure in the synthesis vessel and further modification of this type of procedure on the solids properties were studied. It was found that SiO₂–ZrO₂ and SiO₂–TiO₂ mixed oxides dried at atmospheric pressure developed type I isotherms. On the other hand, for the SiO₂–ZrO₂ and SiO₂–TiO₂ mixed oxides that were treated under pressure in the autoclave (at high SiO₂ content) the porosity was improved and mesoporous materials exhibiting type IV adsorption isotherms. Specific surface area and pore size distribution were a function of ZrO₂ and TiO₂ content. The materials exhibited narrow pore size distributions with pore diameters in the region of mesopores at about 4 nm and high surface areas, the highest being 481 m²/g for the 10 wt% ZrO₂ Si–Zr material. Differences in acidity as determined by pyridine thermodesorption were observed to depend on the synthesis parameters and ZrO₂ and TiO₂ concentration.     

Fabrication by stereolithography of fiber-reinforced fused silica composites with reduced crack and improved mechanical properties

Chopped quartz fiber-reinforced fused silica (SiO_2f/SiO₂) composites were fabricated by stereolithography. The fiber orientation characteristics and crack distributions after the debinding process of the green bodies were investigated. The results showed that the distribution of fibers presented orientation characteristics; additionally, the number of cracks after debinding decreased as the fiber content increased and the cracks oriented along the fiber orientation. The mechanical properties of SiO_2f/SiO₂ ceramics with different fiber contents were also considered. As a result, a compressive strength of 51.2 MPa and flexural strength of 24.3 MPa were achieved for the SiO_2f/SiO₂ ceramic with 4 wt% fiber, and a sintered cambered structure with a size over 150 mm × 150 mm × 3 mm was fabricated successfully without cracking and deformation for the SiO_2f/SiO₂ composites with a fiber content of 4 wt% and 6 wt%.