Photo-induced super-hydrophilic property and photocatalysis on transparent Ti-containing mesoporous silica thin films

The transparent Ti-containing mesoporous silica thin films can be prepared on quartz plate using a spin-coating sol–gel method. The spectroscopic characterization has revealed that the Ti-containing mesoporous silica thin films contain isolated and tetrahedrally-coordinated titanium oxide moieties in the frameworks. Compared with the common mesoporous silica thin films, these Ti-containing mesoporous silica thin films have demonstrated a strong hydrophilic surface property even before UV-irradiation. After UV-light irradiation, the contact angle of water droplet on the Ti-containing mesoporous silica thin films became lower, indicating the appearance of the super-hydrophilic property. Under UV-light irradiation Ti-containing mesoporous silica thin films also exhibited highly selective activity for the photocatalytic oxidation of propylene. The isolated and tetrahedrally-coordinated titanium oxide moieties are responsible for these photo-induced surface reactions.     

Highly active Ti-rich ordered mesoporous titanium silicate synthesizedunder strong acidic condition

Titanium-rich highly ordered mesoporous silica has been synthesized by using unconventional Ti source TiCl₄ under strongly acidic pH condition in the presence of a cationic surfactant as supramolecular structure directing agent (SDA). The most Ti-rich sample for these mesoporous titanium silicates with two-dimensional hexagonal ordered structure was observed with Si/Ti=7.6 in the product. XRD, N₂ sorption, ²⁹Si MAS NMR, UV-vis diffuse reflectance, FT-IR spectroscopic tools, TEM and SEM image analyses were employed to characterize these materials. BET surface area and mesopore volume for all the samples were high. Strong UV-vis absorption band at 222 nm and FT-IR stretching vibration band of Si-O-Ti at were observed in these Ti-rich samples indicating the presence of titanium in isolated tetrahedral environment and strongly bound inside the mesoporous framework. These Ti-rich ordered mesoporous titanium silicate samples showed excellent catalytic activity in the epoxidation of styrene (sample 2 having Si/Ti=7.6 showed 86% conversion with ca. 85% selectivity for styrene oxide) using dilute aqueous H₂O₂ as oxidant.     

Synthesis, characterization and photocatalytic reactivity of Ti-containing micro- and mesoporous materials

Ti-oxides incorporated within the framework of microporous zeolites and mesoporous molecular sieves were found to exhibit high and unique photocatalytic activity for the decomposition of NO into N₂ and O₂ as well as the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH. Spectroscopic investigations of these catalytic systems using photoluminescence, UV-vis, XAFS (XANES and FT-EXAFS) and IR analyses revealed that the charge transfer excited state of the isolated tetra-coordinated Ti-oxides plays a vital role in these photocatalytic reactions. The reactivity of such Ti-oxides was found to depend strongly on their local structures which were controlled by the unique framework structures of the micro- and mesoporous material supports.     

Efficient adsorption and photocatalytic degradation of organic pollutants diluted in water using the fluoride-modified hydrophobic titanium oxide photocatalysts: Ti-containing Beta zeolite and TiO2 loaded on HMS mesoporous silica

Using the F⁻ media, the hydrophobic zeolite and mesoporous silica can be synthesized. These hydrophobic porous materials exhibit the high ability for the adsorption of organic compounds diluted in water and become the useful supports of photocatalyst. The hydrophobic Ti-Beta(F) zeolite prepared in the F⁻ media exhibited high efficiency than the hydrophilic Ti-Beta(OH) zeolite prepared in OH⁻ media for the liquid-phase photocatalytic degradation of 2-propanol diluted in water to produce CO₂ and H₂O. The TiO₂ loaded on the hydrophobic mesoporous silica HMS(F) (TiO₂/HMS(F)), which was synthesized using tetraethyl orthosilicate, tetraethylammonium fluoride as the source of the fluoride and dodecylamine as templates, also exhibited the efficient photocatalytic performance for the degradation. The amount of adsorption of 2-propanol and the photocatalytic reactivity for the degradation increased with increasing the content of fluoride ions on these photocatalysts. The efficient photocatalytic degradation of 2-propanol diluted in water on Ti-Beta(F) zeolite and TiO₂/HMS(F) mesoporous silica can be attributed to the larger affinity for the adsorption of propanol molecules on the titanium oxide species depending on the hydrophobic surface properties of these photocatalysts.     

The use of an impure inorganic precursor for the synthesis of highly siliceous mesoporous materials under acidic conditions

Highly ordered mesoporous silica materials have been synthesized under acidic conditions using an industrial waste-product containing only 42 wt% silica as the precursor, using formic acid as pH-regulator. Non-ionic tri-block-co-polymers of the ABA type were used as the structure-directing agents, and high-quality SBA-15 and KIT-5 materials were obtained. The materials were characterized by small-angle X-ray diffraction, nitrogen physisorption, transmission electron microscopy, and elemental analysis. The methodology presented here is suggested to be widely applicable for the synthesis of siliceous materials using other impure inorganic silica precursors with different purity, as long as the precursors are soluble under acidic conditions.     

Synthesis, structural characterization and photocatalytic activity of Ti-MCM-41 mesoporous molecular sieves

This paper reports the applicability of hydrothermal synthesis in alkaline medium for preparation of Ti-containing mesoporous MCM-41 materials. The influence of different parameters was investigated, such as the Ti source, the molar ratio between Si and Ti and also the synthesis temperature. Structural analysis shows that the high specific surface area, large pore size and well ordered mesostructure, are partially retained in the titania containing materials. Modifying synthesis temperature, it was shown that MCM-41 isotherms are different for temperatures above or under 140°C. UV-VisDR spectroscopy was used to investigate the local environment of Ti sites. The obtained materials were evaluated for the photocatalytic degradation of Rhodamine 6G in aqueous medium. The best photocatalytic activity was found for the sample prepared at higher ageing temperature of 160°C, at which anatase particles were formed.     

Synthesis of ordered small pore mesoporous silicates with tailorable pore structures and sizes by polyoxyethylene alkyl amine surfactant

Ordered mesoporous silicates with tailorable pore structures and small pore sizes have been synthesized by using polyoxyethylene alkyl amine surfactant PN-430 [CH₃(CH₂)₁₇N(EO)_x(EO)_y, x + y = 5] as a structure-directing agent under acidic condition. Two-dimensional (2-D) hexagonal (p6mm) mesoporous silicates have been prepared via an evaporation-induced self-assembly (EISA) process. The N₂ sorption isotherms show that the product has a small uniform pore size distribution of 1.8 nm by BJH model, a BET surface area of 730 m²/g and a pore volume of 0.36 cm³/g. 3-D cubic (Pm-3n) mesoporous silicate with small uniform pore size (1.76 nm) can also be prepared at high concentration of PN-430 by EISA method in tetrahydrofuran solvent. The solvothermal post-treatment by n-hexane at 70 °C for 3 d to the above material results in the phase transition of the mesostructure from Pm-3n to P6₃/mmc based on XRD and TEM analyses. In comparison, by using nonionic oligometric alkyl-ethylene oxide surfactant such as Brij 78 (C₁₈H₃₇EO₂₀) or Triton X-100 (CH₃C(CH₃)₂CH₂C(CH₃)₂C₆H₄ EO₁₀) as co-templates, high-quality hexagonal (p6mm) small pore mesoporous silicates have also been prepared in ethanol media. Our results show that the blend templates composed of PN-430 and a small amount of nonionic surfactant can increase the efficiency of organic and inorganic hybrid species assembly, improve the quality of the structural regularity, and decrease the pore size to about 1.65 nm.     

Room temperature synthesis of spherical mesoporous titania

This work reports a facile hydrolysis method for the synthesis of spherical mesoporous titania particles using titanium tetrachloride under mild conditions. The method can be easily controlled or expanded. The influences of various reaction conditions including concentration of Ti⁴⁺ ions and water content on the formation of mesoporous titania particles were systematically investigated. The titania particles were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), high-resolution transmission electron microscopy (HRTEM) and Brunauer-Emmett-Teller (BET) surface areas. Experimental results showed that the mesoporous titania particles have special surface structure and excellent thermally stable mesoporous structure after annealing at high temperatures (500 °C). The effects of various reaction conditions, such as concentration of Ti⁴⁺, H₂O/n-butanol volume ratio and reaction temperature, on formation, crystal phase, morphology of titania particles were investigated.     

Synthesis of morphology-controlled mesoporous transition aluminas derived from the decomposition of alumina hydrates

Aluminum hydroxides were synthesized through the acidification of sodium aluminate solution using single organic diester or diacid as pH adjustor and aluminum chelating agent. The obtained alumina hydrates are investigated by XRD, SEM, IR and TG. Bayerite firstly formed at room temperature, and its morphology greatly varied with the pH adjustors used, which probably attributes to different kinetics of the acidification. The bayerite can evolve to gibbsite and boehmite after the hydrothermal treatment at 100 °C and 145 °C, respectively, where these alumina hydrates show diverse morphologies. After the calcination, these alumina hydrates of bayerite, gibbsite and boehmite could pseudomorphically transform to the corresponding η-, χ- and γ-aluminas, respectively, exhibiting different structural and textural properties. Interestingly, the transition aluminas derived from the aluminum tri-hydroxides, bayerite and gibbsite, both display locally organized mesopores, while no such meso-structure can be observed in γ-alumina obtained from the aluminum mono-hydroxide, boehmite. The changes of bayerite during calcination are investigated detailed. The dehydration of non-porous bayerite accompanied with the formation of meso-structured transition aluminas, where the meso-structure becomes more and more clearly defined and pore size expands with the calcination temperature increasing.     

Synthesis of mesoporous calcium phosphate using hybrid templates

Mesostructured calcium phosphate was synthesized by means of the combination of a soluble metal salt with an aqueous phenylphosphonic acid solution containing sodium dodecyl sulfate (SDS). Phenylphosphonic acid (PhP) was selected as the template to pattern the materials with pores generated by the formation of a lamellar calcium PhP phase. SDS was introduced to improve the thermal stability of the pore structure. The resulting materials were characterized by means of X-ray diffraction (XRD), small-angle X-ray diffraction (SAXS), electron microscopes and BJH gas absorption method. With the aid of SDS, calcium phosphate materials with the surface area and pore volume as 72 m²/g and 569 cm³/g, respectively, were successfully developed at the SDS:PhP molar ratio of 0.3:1. It was found that the addition of SDS could effectively improve the thermal stability of the pore structure. A possible mechanism was proposed to interpret the formation procedure and the improved thermal stability of the mesoporous structure.     

Synthesis of a mesoporous material from two natural sources

Mesoporous materials were obtained from two natural silica sources, diatomite and pumicite, under hydrothermal conditions, autogenic pressure and in presence of the surfactant cetyltrimethylammonium bromide (CTAB) as the template. Using diatomite, a temperature of 383 K and the following molar ratios in the initial reaction gel: SiO₂/Al₂O₃ = 8.86; CTAB/SiO₂ = 0.1; Na₂O/SiO₂ = 0.10–0.25 and H₂O/Na₂O = 250–300, the mesoporous material MCM‐41 was obtained in a reaction time of 48 h. When pumicite was used, a mesoporous material was obtained in a reaction time of 96 h, a reaction temperature of 423 K and an initial reaction gel with the following molar ratios: SiO₂/Al₂O₃ = 8.86; CTAB/SiO₂ = 0.1; Na₂O/SiO₂ = 0.25 and H₂O/Na₂O = 330. Copyright © 2006 Society of Chemical Industry     

Ethylene epoxidation on Ag catalysts supported on non-porous, microporous and mesoporous silicates

The ethylene epoxidation activity of Ag catalysts supported on non-porous SiO₂, microporous silicalite zeolite and mesoporous MCM-41 and HMS silicates was investigated in the present study in comparison to conventional low surface area -Al₂O₃ based catalysts. The MCM-41 and HMS based catalysts exhibited similar ethylene conversion activity and ethylene oxide (EO) selectivity with the SiO₂ and -Al₂O₃ based catalysts at relatively lower temperatures (up to 230 °C), whereas their activity and selectivity decreased significantly at higher temperatures (≥300 °C). The silicalite based catalyst was highly active for a wide temperature range, similar to the SiO₂ and -Al₂O₃ based catalysts, but it was the less selective amongst all catalysts tested. High loadings of Ag particles (up to ca. 40 wt.%) with medium crystallites size (20–55 nm) could be achieved on the mesoporous materials resulting in very active epoxidation catalysts. The HMS-type silicate with the 3D network of wormhole-like framework mesopores (with average diameter of 3.5 nm), in combination with a high-textural (interparticle) porosity, appeared to be the most promising mesoporous support.     

Synthesis, characterization and photocatalytic reactivity of Ti-containing micro- and mesoporous materials

Ti-oxides incorporated within the framework of microporous zeolites and mesoporous molecular sieves were found to exhibit high and unique photocatalytic activity for the decomposition of NO into N₂ and O₂ as well as the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH. Spectroscopic investigations of these catalytic systems using photoluminescence, UV-vis, XAFS (XANES and FT-EXAFS) and IR analyses revealed that the charge transfer excited state of the isolated tetra-coordinated Ti-oxides plays a vital role in these photocatalytic reactions. The reactivity of such Ti-oxides was found to depend strongly on their local structures which were controlled by the unique framework structures of the micro- and mesoporous material supports.     

Facile template-free synthesis of meso-macroporous titanium phosphate with hierarchical pore structure

Meso-macroporous titanium phosphate materials with hierarchical structure have been synthesized through a facile and template-free method using titanium n-butoxide (TBT) as titanium source. Both the as-synthesized titanium phosphate and the sample after calcination at 500 °C are amorphous, as proved by the XRD measurements. The co-existence of mesopores and macropores is identified by N₂ adsorption–desorption measurements, SEM and TEM methods. The formation of Ti–O–P bonds during the synthesis process was supported by FT-IR spectroscopy, and was further verified by ³¹P MAS NMR spectra and XPS measurements. The BET surface area of the products can be adjusted by addition of n-butanol.     

Synthesis of metal-incorporated mesoporous crystalline silicates for oligomerization of propene

Mesoporous crystalline silicates were synthesized with incorporation of various metal components such as Al, Ga, or Fe. Mesoporous silicate synthesized without metal incorporation showed the highest thermal stability. Although the thermal stability was weakened by metal incorporation, Al- and Fe-mesoporous-silicate with lower metal content (Si/metal atomic ratio of 200) maintained the high surface area about 600 m²/g after the calcination at 1000°C for 0.5 h. Even when the same surfactant (dodecyltrimethylammonium bromide) was used as template, the pore diameter and wall thickness were changed by the gel mixture composition and the thermal stability of mesoporous silicates could be enhanced by increase in wall thickness. The catalytic activity of Al-mesoporous-silicate was also increased with an increase in pH of the gel mixture before crystallization. Although the catalytic activity of mesoporous silicate was lower than the activities of the other zeolitic catalysts like ZSM-5, a considerable amount of oligomers was produced from propene even at the lower temperature range and the possibility for the production of larger organic molecules could be confirmed.     

Synthesis and inorganic conversion of polyborodiphenylsiloxane

Polyborodiphenylsiloxane (PPBSO) was reported to play significant roles in the preparation of advanced SiC ceramics as a precursor initiator, sintering binder and boron introducer. However, neither the effect of this important raw material on the pyrolysis process nor the evolution of boron has been clarified. This study synthesized PPBSO as a preceramic polymer and thoroughly investigated the constitutional and structural evolutions during organic-to-inorganic conversion. Boron was found to transform into the B(OSi)₃ structure fully at 1300 °C, and this structure played an important role in increasing the Si content (from 18.51%_wt to 35.84%_wt) by forming a viscous fluid barrier that reduced the gaseous release, which led to an increase in the vapor pressure and a reduction in the Si–O–C phase decomposition according to the Le Chatelier principle. The dominant B–O–C phase that was observed at 1000 °C transformed into a B(OSi)₃ structure, and high-pressure-formed BC₄, detected via Raman spectroscopy, was the result of the partial pressure increase. A crystallization-promoting effect of free carbon in the presence of boron was also detected via Raman analysis. This study extensively describes the role of boron in the silicon carbide ceramic conversion process and will be of substantial benefit for the fabrication of high-performance ceramic materials.     

Aqueous route for mesoporous metal oxides using inorganic metal source and their applications

In this paper, we report a synthetic route for mesoporous metal oxides from inorganic metal sources in aqueous media. This synthesis route offers a versatile, low cost and environmental friendly method to produce mesoporous metal oxides that have very high surface areas. As an example, the synthesis of iron oxide is described in detail. Synthesis conditions including aging time, aging temperature and amount of urea were varied to find the optimal synthesis conditions. We found that recycling the Cetyltrimethylammonium Bromide (CTAB) template is possible when the amount of urea is reduced to stoichiometric. The mesoporous metal oxides made under these conditions are self assemblies of leaf-like single crystal sub-units with randomly distributed mesopores embedded into the crystals. As a result of the crystalline nature, these mesoporous metal oxides have high thermal stabilities and their applications as gas sensors and CO disproportionation catalysts indicate promising aspects of these materials.     

Selective formation of CH3OH in the photocatalytic reduction of CO2 with H2O on titanium oxides highly dispersed within zeolites and mesoporous molecular sieves

Highly dispersed titanium oxide catalysts have been prepared within zeolite cavities as well as in the zeolite framework and utilized as photocatalysts for the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH at 328 K. In situ photoluminescence, ESR, diffuse reflectance absorption and XAFS investigations indicate that the titanium oxide species are highly dispersed within the zeolite cavities and framework and exist in tetrahedral coordination. The charge transfer excited state of the highly dispersed titanium oxide species play a significant role in the reduction of CO₂ with H₂O with a high selectivity for the formation of CH₃OH, while the catalysts involving the aggregated octahedrally coordinated titanium oxide species show a high selectivity to produce CH₄, being similar to reactions on the powdered TiO₂ catalysts. Ti-mesoporous molecular sieves exhibit high photocatalytic reactivity for the formation of CH₃OH, its reactivity being much higher than the powdered TiO₂ catalysts. The addition of Pt onto the highly dispersed titanium oxide catalysts promotes the charge separation which leads to an increase in the formation of CH₄ in place of CH₃OH formation.     

Synthesis of mesoporous alumina TUD-1 with high thermostability

Mesoporous alumina, TUD-1, was prepared via a sol-gel process by using tetraethylene glycol (TEG) as template. The effect of TEG and solvents on the pore structure of the final products was studied. A mechanism using non-surfactant template was proposed. It was found that TUD-1 has amorphous framework, high surface area, large pore volume and narrow pore size distribution together with high thermal stability upon prolonged heat treatment at high temperatures, which is essential for applications in adsorption and catalysis.     

Synthesis of mesoporous ZnS synergistically templated by butylamine and alkanols

Pore size and pore volume adjustable mesoporous ZnS was synthesized through a co-template method, which was achieved by the combined interaction between butylamine and some alkanols with proper lengths of the straight carbon chain. The pore size for mesoporous ZnS templated by butyl amine alone was 4.29 nm, and could be enlarged to 6.96 and 8.33 nm respectively through adding certain amounts of hexanol and octanol. Correspondingly, the pore volume also exhibited an augmentation with increasing carbon chain lengths of alkanols from C₆ to C₈. However, the pore size and pore volume dropped abruptly when decanol was added as the auxiliary agent. The formation of mesopores for ZnS prepared using butylamine molecules as the only templating agent is considered to be attributed to the coordination between N atoms in amines and Zn²⁺ ions at the surfaces of zinc suphide. The templating effect of butylamines might be improved by adding hexanols and octanols to form aggregates through solubilization to tailor the pore size and pore volume of ZnS effectively, while the function of decanols for changing the porous structure is restricted by its low solubility.