Characterization and catalytic properties of nickel-substituted hexagonal mesoporous silica prepared by microwave-hydrothermal method

The liquid phase of acetylation of 1,2-dimethoxybenzene with acetic anhydride has been investigated over a series of acid nickel-mesoporous materials (Ni-MCM-41) synthesized by the microwave irradiation method with different Si/Ni ratios (Si/Ni = 80, 50, 10) and characterized by several spectroscopic techniques such as: N₂ physical adsorption, ICP, XRD, TEM, FT-IR, and a temperature programmed desorption (TPD) of pyridine. In fact, the catalyst Ni-MCM-41 (10) showed better performance in the acid-catalyzed acetylation of 1,2-dimethoxybenzene employing acetic anhydride as an acylating agent. Furthermore, the kinetics of the acetylation of 1,2-dimethoxybenzene over these catalysts have also been investigated.     

Study of photocatalytic activity of Cd-doped mesoporous nanocrystalline TiO2 prepared at low temperature

Mesoporous nanocrystalline Cd-doped titania was firstly prepared at low temperature by a modified sol–gel method, using dodecylamine as a template. The template could be easily removed by refluxing samples in nitric acid ethanol solution. The Fourier transform infrared spectrometer (FT-IR), low-angle and wide-angle X-ray diffraction (XRD), N₂ adsorption–desorption, transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and UV–visible diffuse reflectance spectroscopy were used for the characterization of catalysts. The characteristic results clearly showed that Cd²⁺ ions were doped into the titania lattice, and the mesoporous architecture of Cd-doped TiO₂ was composed of mixed-phase crystal textures of anatase and brookite. The samples displayed high visible-light photocatalytic activity for photodegradating 2,4-dichlorophenol (2,4-DCP) solution. The high activities of samples were attributed to the bicrystalline framework, large BET surface area, small crystallite size, and Cd-doping.     

Effect of calcination atmosphere on the structure and photocatalytic properties of titania mesoporous powder

In the work presented here, mesoporous titania (MTO) powders are synthesised by the sol?Cgel method using amphiphilic triblock copolymer as a template in two different calcination atmospheres, N₂ and air. Various techniques such as sequential thermal analysis (STA), small-angle X-ray diffraction (SAXRD), wide-angle X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet (UV)?Cvisible spectroscopy, high-resolution transmission electron microscopy (HRTEM) and N₂-adsorption/desorption analysis were utilised to study the prepared samples. Furthermore, the photocatalytic activities of the prepared samples were evaluated from the photo-degradation analysis of methylene blue (MB). For the sample calcined at N₂, the formation of an ordered mesostructure with a high specific surface area (172?m²?g^?1), mesoporosity (48%) and enhanced photocatalytic activity were obtained compared to that of the sample calcined in air. The observed increased MB degradation for the latter is mainly attributed to the formation of higher specific surface area and mesoporosity. The availability of highly ordered open-pore channels could provide increased contacts between reactants in the solution and the active sites on the surface of titania mesoporous particles. Considering the photoactivities of the samples, it is revealed that the photocatalytic activity is enhanced, together with an increase in the surface defects in N₂ atmosphere.     

Cerium-doped mesoporous BaTiO3/TiO2 nanocomposites: structural,optical and photocatalytic properties

Research on Chemical Intermediates - Nanoscale composite materials based on cerium, barium titanate and titanium dioxide were synthesized by thermal hydrolysis. The obtained individual TiO2, BaTiO3...     

Synthesis and photocatalytic properties of highly crystalline and ordered mesoporous TiO2 thin films

Highly crystalline and ordered mesoporous TiO2 thin films have been synthesized by stabilization of the mesostructure with confined carbon; the films exhibit 2.5% photoconversion efficiency for the water photolysis at zero-bias and Xe lamp illumination of 40 mW cm(-2).     

Synthesis and photocatalytic activity for water-splitting reaction of nanocrystalline mesoporous titania prepared by hydrothermal method

Nanocrystalline mesoporous TiO₂ was synthesized by hydrothermal method using titanium butoxide as starting material. XRD, SEM, and TEM analyses revealed that the synthesized TiO₂ had anatase structure with crystalline size of about 8 nm. Moreover, the synthesized titania possessed a narrow pore size distribution with average pore diameter and high specific surface area of 215 m²/g. The photocatalytic activity of synthesized TiO₂ was evaluated with photocatalytic H₂ production from water-splitting reaction. The photocatalytic activity of synthesized TiO₂ treated with appropriate calcination temperature was considerably higher than that of commercial TiO₂ (Ishihara ST-01). The utilization of mesoporous TiO₂ photocatalyst with high crystallinity of anatase phase promoted great H₂ production. Furthermore, the reaction temperature significantly influences the water-splitting reaction.     

Characterization and acidic properties of Al-SBA-15 materials prepared by post-synthesis alumination of a low-cost ordered mesoporous silica

A series of Al-containing SBA-15 type materials with different Si/Al ratio, were prepared by post-synthesis modification of a pure highly ordered mesoporous silica SBA-15 obtained by using sodium silicate as silica source, and amphiphilic block copolymer as structure-directing agent. A high level of aluminum incorporation was achieved, reaching an Si/Al ratio of up to 5.5, without any significant loss in the textural properties of SBA-15. These materials were fully characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ²⁷Al NMR spectroscopy, and N₂ adsorption at 77 K. The acid properties of these materials have been evaluated by NH₃-TPD, adsorption of pyridine and deuterated acetonitrile coupled to FTIR spectroscopy. The effective acidity of these materials was evaluated using two catalytic reactions: 2-propanol dehydrogenation and 1-butene isomerization. The adsorption of basic probe molecules and the catalytic behavior revealed an evolution of the acid properties with the Al content. These studies have shown that the Al-SBA-15 materials contain Brønsted and Lewis acid sites with medium acidity which makes them appropriate to be used as acid catalysts in heterogeneous catalysis, catalytic supports, and adsorbents.     

Long TiO2 hollow fibers with mesoporous walls: sol-gel combined electrospun fabrication and photocatalytic properties

Long TiO2 hollow fibers with mesoporous walls have been fabricated with the sol-gel combined two-capillary spinneret electrospinning technique using a triblock copolymer (Pluronic, P123, (H(C2H5O)20(C3H7O)70 (C2H5O)20OH) as a pore-directing agent. The as-prepared hollow fibers were as long as 30 cm with an outer diameter of 0.1-4 microm and wall thickness of 60-500 nm. The diameters and wall thicknesses of the hollow fibers could be tuned by adjusting the electrospinning parameters. The fiber walls were composed of mesopores 6.7 nm in diameter as calculated from the N2 adsorption/desorption isotherm. The high-resolution TEM (HR-TEM) images exhibited that the mesopores were hexagonally aligned with a low order because of the curving of the pores. When comparing with other nanostructured TiO2 materials such as commercial TiO2 nanoparticles (P25, Degussa) and mesoporous TiO2 powders, the hollow fibers exhibited higher photocatalytic activities toward degradation of methylene blue and gaseous formaldehyde.     

Characterization of Zr-doped TiO2 nanocrystals prepared by a nonhydrolytic sol-gel method at high temperatures

Highly crystalline and surface-modified Zr-doped TiO(2) nanorods were successfully prepared using a nonhydrolytic sol-gel method that involves the condensation of metal halides with alkoxides in anhydrous trioctylphosphine oxide (TOPO) at either 320 or 400 degrees C. In addition, the interaction of the cross-condensation between the Ti and Zr species was studied by characterizing the morphologies, crystalline structures, chemical compositions, surface properties, and band gaps of the nanocrystals obtained at different reaction temperatures and Zr-to-Ti stoichiometric ratios. Increases in the concentration of Zr(4+) and in the reaction temperature led to large nanorods and regular shapes, respectively. In addition, only the anatase form was observed in the Zr-doped TiO(2) nanorods. The Zr-to-Ti ratios obtained ranged from 0.01 to 2.05, all of which were far below the stoichiometric ratios used during the preparation of the samples (0.25-4). Moreover, the Zr(4+) units accumulated mainly at the surface of the TiO(2) nanocrystals. The band gaps of the Zr-doped TiO(2) nanorods ranged from 2.8 to 3.8 eV, which are smaller than those of pure TiO(2) (3.7 eV) or ZrO(2) (5.2 eV). The Zr-doped anatase TiO(2) nanorods prepared at 400 degrees C at an initial stoichiometric Zr-to-Ti ratio of 2:3 exhibited the highest photoactivities for the decomposition of rhodamine B because of the presence of trace amounts of Zr(4+) (Zr/Ti = 0.03) in the TiO(2) and the regular shapes of these particles. DSC analysis indicated that the temperatures for forming nanocrystalline TiO(2) and ZrO(2) were 207 and 340 degrees C, respectively. Moreover, the reactivities of condensation between the Ti species were reduced when Zr species were involved in the NHSG reactions. The results obtained in this study clearly demonstrate that the faster kinetics for the generation of TiO(2) controls the material properties as well as the photoactivities of the nonhydrolytic sol-gel-derived nanocrystals.     

Design of hierarchical porous aluminas by using one-pot synthesis and different calcination temperatures

Hierarchical aluminas with pore sizes ranging from a few nanometers to micrometers were obtained using an one-pot sol?Cgel synthesis. The aluminas were synthesized under acid conditions from aluminum isopropoxide in presence of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer template and decahydronaphthalene as emulsifier agent. High-resolution transmission electron microscopy, small-angle X-ray scattering, nitrogen physisorption isotherms and mercury intrusion porosimetry provided evidences of porous structure at different hierarchical levels. The produced aluminas possess hierarchical structure composed of different family of pores that coexist in form of cylinders, pyramids and stacking of platelets. The morphology observed by electron microscopy suggests that the cylindrical pores result from the stacking platelets and that the cylinders and pyramidal pores form the walls of macropores of circular section. These aluminas with hierarchical porous architecture present large surface areas (ca. 435?m² g^?1) and pore volumes (ca. 2.1?cm³ g^?1), tunable pore-size distributions and good thermal stability.     

The improved photocatalytic properties of P-type NiO loaded porous TiO2 sheets prepared via freeze tape-casting

For the interest of the practical application, porous TiO₂ sheets were prepared by a novel freeze tape-casting method, in order to improve the photocatalytic activities of these TiO₂ sheets, p-type NiO was loaded by chemical solution deposition. The samples were characterized by a series of physical means, including XRD, SEM, EDS, XPS, ICP-OES, and UV-vis spectroscopy. The photocatalytic activities of the samples were evaluated by the degradation of methyl orange solution. The results showed that the photocatalytic activity of the TiO₂ sheet was greatly enhanced by the NiO loading, and the photocatalytic efficiency increased with increasing the NiO loading, the extraordinary performance for the NiO-loaded sample with 0.1 M precursor dipped was related to its unique morphology. The sample annealed at 600 °C showed the better photocatalytic activity than the sample annealed at 400 °C and 800 °C. The improvement of the photocatalytic activity was attributed to the formation of p–n junctures at the interface of the NiO/TiO₂, which facilitates the photoinduced electron/hole pairs' separation by the inner electric field, thus leading to the higher photocatalytic activities for the NiO-loaded TiO₂ sheets.     

Photocatalytic properties of Zn2SnO4 powders prepared by different modified hydrothermal routes

Research on Chemical Intermediates - In this work, different synthesis methods of zinc stannate (Zn2SnO4–ZTO) were proposed in order to obtain a material with a...     

Optimizing the photocatalytic properties of hydrothermal TiO2 by the control of phase composition and particle morphology. a systematic approach

The possibility of controlling the photocatalytic activity of TiO2 nanoparticles by tailoring their crystalline structure and morphology is a current topic of great interest. In this study, a broad variety of well-faceted particles with different phase compositions, sizes, and shapes have been obtained from concentrated TiOCl2 solutions by systematically changing temperature, pH, and duration of the hydrothermal treatment. The guide to select the suitable experimental conditions was provided by thermodynamic modeling based on available thermochemical data. By combining the results of TEM, HRTEM, XRD, density, and specific surface area measurements, a complete structural and morphological characterization of the particles was performed. Correlation between the photocatalytic activity in the UV photodegradation of phenol solutions and the particle size was established. Prismatic rutile particles with length/width ratio around 5 and breadth of 60-100 nm showed the highest activity. The surface chemistry of the particles was also investigated. Treatments that decrease the surface acidity, such as washing the powders with ammonia solution and/or calcining at 400 degrees C, have detrimental effect on photocatalytic activity. The overall results suggest correlation between particle morphology and photocatalytic activity and indicate that both electron-hole recombination and adsorption at the surface can be rate-controlling processes. The systematic approach presented in this study demonstrates that a substantial improvement of the photocatalytic activity of TiO2 can be achieved by a careful design of the particle morphology and the control of the surface chemistry.     

Photocatalytic and antifouling properties of TiO2-based photocatalytic membranes

Photocatalysis has been extensively studied due to its potential ability to avoid the excessive use of chemical reagents and reduce the energy consumption by employing solar energy. Moreover, to alleviate the reduction in the membrane permeation selectivity, separation efficiency, and membrane service life caused by the emerging micro-pollutants and membrane fouling, membrane technology is often coupled with microbial, electrochemical, and catalytic processes. However, although physical/chemical cleaning and membrane module replacement can overcome the inherent limitations caused by membrane fouling and other membrane separation processes, high operating costs limit their practical applications. In this review, common preparation methods for TiO₂ photocatalytic membranes are described in detail, and the main approaches to enhancing their photocatalytic performance are discussed. More importantly, the mechanism of the TiO₂ photocatalytic membrane antifouling process is elucidated, and some applications of photocatalytic membranes in other areas are described. This review systematically outlines future research directions in the field of photocatalytic membrane modification, including metal and non-metal doping, fabrication of heterojunction structures, control over reaction conditions, increase in hydrophilicity, and increase in membrane porosity.     

Polyacrylamide gel synthesis and photocatalytic properties of TiO2 nanoparticles

In this study, a polyacrylamide gel route was introduced to synthesize TiO₂ nanoparticles. The influence of synthesis conditions on the properties of products was investigated. It is found that the samples prepared at the calcination temperature of 400 °C crystallize majorly in the anatase phase with a minor rutile phase. The second rutile phase has a dependence on the chelating agent, which is formed more readily when using acetic acid as the chelating agent. The introduction of acrylamide and glucose to the precursor solution shows the capability of improving the particle morphology, and the resulted particles are uniformly shaped like spheres. The photocatalytic activity of the prepared TiO₂ samples was evaluated by the degradation of acid orange 7 under 254 nm ultraviolet irradiation, revealing that they exhibit a good photocatalytic activity. Ethanol was used as a ^·OH scavenger to investigate its effect on the photocatalytic efficiency as well as the ^·OH radical yields. Based on the experimental results, ^·OH radical is suggested to be the dominant active species responsible for the dye degradation.     

High-temperature synthesis of highly hydrothermal stable mesoporous silica and Fe-SiO2 using ionic liquid as a template

Mesoporous silicas and Fe-SiO₂ with worm-like structures have been synthesized using a room temperature ionic liquid, 1-hexadecane-3-methylimidazolium bromide, as a template at a high aging temperature (150-190 °C) with the assistance of NaF. The hydrothermal stability of mesoporous silica was effectively improved by increasing the aging temperature and adding NaF to the synthesis gel. High hydrothermally stable mesoporous silica was obtained after being aged at 190 °C in the presence of NaF, which endured the hydrothermal treatment in boiling water at least for 10 d or steam treatment at 600 °C for 6 h. The ultra hydrothermal stability could be attributed to its high degree of polymerization of silicate. Furthermore, highly hydrothermal stable mesoporous Fe-SiO₂ has been synthesized, which still remained its mesostructure after being hydrothermally treated at 100 °C for 12 d or steam-treated at 600 °C for 6 h.