Preparation of TiO2 nanocrystallites by hydrolyzing with gaseous water and their photocatalytic activity

TiO2 nanocrystallites were prepared front precursors tetra-n-butyl titanate (Ti(OC4H9)(4)) and titanium tetrachloride (TiCl4). The precursors were hydrolyzed by gaseous water in autoclave, and then calcined at predetermined testing temperatures. The samples were characterized by X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (TG-DTA), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectra (FT-IR), and UV-vis diffuse reflectance spectra (DRS). The photocatalytic activities of the samples were evaluated by the photobleaching of methylene blue (MB) in aqueous solution and the photocatalytic oxidation of propylene in gas phase at ambient temperature. The results showed that the anatase phase nanocrystalline TiO2 could be obtained at relatively low temperatures (for precursor Ti(OC4H9)4 at I I VC and for TiCl4 at 140 degrees C, respectively), and that the as prepared samples exhibited high photocatalytic activities to photobleach MB in aqueous solution. As the calcination temperatures increasing. the decolor ratio of MB increased and reached the maximum value of nearly 100% at 600 degrees C, and then decreased. The photobleaching of MB by all samples followed the pseudo-first-order kinetics with respect to MB concentration.

Adsorption and interaction of H2S/SO2 on TiO2

Adsorption and interaction of H2S/SO2 on titania as well as on alumina for comparison has been studied by temperature programmed desorption (TPD), infrared (IR) spectroscopy and temperature programmed electronic conductivity (TPEC) techniques. It was found that the adsorption of both H2S acid SO2 on TiO2 is much greater than on Al2O3. The electronic conductivity of TiO2 measured by TPEC varies significantly as adsorption and desorption takes place on TiO2, showing a strong interaction between TiO2 and adsorbates. At temperature above 200 degrees C, H2S or SO2 adsorbed on TiO2 can be converted into S, H2O and SO2 or SO3. While on the hydrogen treated TiO2, H2S is decomposed into S and H-2, SO2 into S. The active sites on TiO2 surface cannot be so strongly adsorbed by SO2 that it is much more resistant to the sulfation reaction. Unlike TiO2, Al2O3 only provides surface adsorption sites, which can be readily sulfated. The data obtained support one's understanding why TiO2 exhibits a better catalytic performance than that of Al2O3 as a Claus reaction catalyst. (C) 1999 Elsevier Science B.V. All rights reserved.

Epoxidation of styrene on Si/Ti/SiO2 catalysts prepared by chemical grafting

Titania-silica (Ti/SiO2) and silica-titania-silica (Si/Ti/SiO2) catalysts were:prepared by chemical grafting using TiCl4 and tetraethyl orthosilicate (TEOS) as precursors and SiO2 as support. The prepared catalysts were characterized by UV Raman and visible Raman spectroscopies, XRD and the epoxidation of styrene; Ti/SiO2: catalyst grafted with only titanium species is not very active for epoxidation using H2O2 (30%), but is active and-selective when one uses tert-butyl hydroperoxide (TBHP). The catalyst grafted at high temperatures shows better epoxide selectivity. Si/Ti/SiO2 catalyst, the titanium-silica grafted further with TEOS, is active and selective for the epoxidation of styrene using either dilute H2O2 or TBHP, possibly due to the fact that the grafting of Ti/SiO2 with TEOS modifies the coordination structure of titanium and makes the titanium sites of Si-O-Ti-O-Si species less hydrophilic. A characteristic band at 1085cm(-1) due to Ti-O-Si species is detected for the grafted catalysts by UV resonance Raman spectroscopy. Reaction between TiCl4 and SiO2 at high temperatures favors the formation of Ti-O-Si species. Better activity and selectivity to epoxide,is found for the catalysts with more Ti-O-Si species. It is assumed that the active sites are the highly isolated Ti-O-Si species. For Si/Ti/SiO2 catalyst, the gas phase O-2 can participate in the catalytic oxidation of styrene when H2O2 is present ana:ii causes the formation of benzaldehyde. (C) 2000 Elsevier Science B.V. All rights reserved.

Catalytic oxidation of chlorobenzene on supported manganese oxide catalysts

Total oxidation of chlorinated aromatics on supported manganese oxide catalysts was investigated. The catalysts have been prepared by wet impregnation method and characterized by XRD and TPR. Among the catalysts with the supports of TiO(2), Al(2)O(3) and SiO(2), titania supported catalyst (MnO(x)/TiO(2)) gives the highest catalytic activity. MnO(x)/TiO(2) (Mn loading, 1.9 wt.%) shows the total oxidation of chlorobenzene at about 400 degreesC. The activity can be stable for over 82 h except for the first few hours. At lower Mn loadings for MnO(x)/TiO(2), only one reduction peak appears at about 400 degreesC due to the highly dispersed manganese oxide. With the increase of Mn loading, another reduction peak emerges at about 500 degreesC, which is close to the reduction peak of bulk Mn(2)O(3) at 520 degreesC. TPR of the used catalyst is totally different from that of the fresh one indicating that the chemical state of the active species is changed during the chlorobenzene oxidation. The characterization studies of MnO(x)/TiO(2) showed that the highly dispersed MnO(x) is the precursor of the active phase, which can be converted into the active phase, mainly oxychlorinated manganese (MnO(y)Cl(z)), under working conditions of chlorobenzene oxidation. (C) 2001 Elsevier Science B.V. All rights reserved.

Sol-gel derived oxides and mixed oxides catalysts with narrow mesoporous distribution

A novel sol-gel process for preparing oxides and mixed oxides sols from precipitation and peptization process is reported in this article. Inorganic salts are used as raw materials in this study. It is found that the amount of acid has great influence on the stability and particle diameter distribution of the precursor sols. Ultrasonic treatment is used to prepare alumina sol at room temperature. The result of Al-27 NMR shows that there exist Al-13(7+) species in the sol. By controlling the sol particles with narrow particle diameter distribution, alumina, titania and silica-alumina (SA) materials with narrow mesoporous distribution are formed by regular packing of sol particles during gelation without using any templates. The results also show that the structure and particle diameter distribution of precursor sol determine the final materials' texture.

Low-temperature oxidation of CO over Pd/CeO2-TiO2 catalysts with different pretreatments

A comprehensive study of the low-temperature oxidation of CO was conducted over Pd/TiO2, Pd/CeO2, and Pd/CeO2-TiO2 pretreated by a series of calcination and reduction processes. The catalysts were characterized by N-2 adsorption, XRD, H-2 chemisorption, and diffuse-reflectance infrared Fourier transform spectroscopy. The results indicated that Pd/CeO2-TiO2 has the highest activity among these catalysts, whether in the calcined state or in the reduced state. The activity of all of the catalysts can be improved significantly by the pre-reduction, and it seems that the reduction at low temperature (LTR. 150 degrees C) is more effective than that at high temperature (HTR, 500 degrees C), especially for Pd/CeO2 and Pd/TiO2. The catalysts with various supports and pretreatments are also different in the reaction mechanisms for CO oxidation at low temperature. Over Pd/TiO2, the reaction may proceed through a surface reaction between the weakly adsorbed CO and oxygen (Langmuir-Hinshelwood). For Ce-containing catalysts, however, an alteration of reaction mechanism with temperature and the involvement of the oxygen activation at different sites were observed, and the light-off profiles of the calcined Pd/CeO2 and Pd/CeOi-TiO2 show a distortion before CO conversion achieves 100%. At low temperature, CO oxidation proceeds mainly via the reaction between the adsorbed CO on Pd-0 sites and the lattice oxygen of surface CeO2 at the Pd-Ce interface, whereas at high temperature it proceeds via the reaction between the adsorbed CO and oxygen. The high activity of Pd/CeO2-TiO2 for the low-temperature CO oxidation was probably due to the enhancements of both CO activation, caused by the facilitated reduction of Pd2+ to Pd-0, and oxygen activation, through the improvement of the surface oxygen supply and the oxygen vacancies formation. The reduction pretreatment enhances metal-support interactions and oxygen vacancy formation and hence improves the activity of CO oxidation. (c) 2005 Elsevier Inc. All rights reserved.