Effect of carbon doping on the mesoporous structure of nanocrystalline titanium dioxide and its solar-light-driven photocatalytic degradation of NOx

Effective mesoporous nanocrystalline C-doped TiO(2) photocatalysts were synthesized through a direct solution-phase carbonization using titanium tetrachloride and diethanolamine as precursors. X-ray photoelectron spectroscopy (XPS) results revealed that oxygen sites in the TiO(2) lattice were substituted by carbon atoms and formed a C-Ti-O-C structure. The absorption region of the as-prepared TiO(2) was extended to the visible light region in view of the substitution for oxygen sites by carbon atoms. The photocatalytic activities of the as-prepared samples were tested in a flow system on the degradation of NO at typical indoor air levels under simulated solar-light irradiation. The samples showed a more effective removal efficiency than commercial photocatalyst (P25) on the degradation of the common indoor pollutant NO. The parameters significantly affecting the mesoporous structure and removal efficiency on indoor air were also investigated.     

Synthesis of titanium oxide structures on mesoporous silicon dioxide surface by molecular layering

The formation of titanium oxide structures through the repeated successive treatment of SBA-15 mesoporous silicon dioxide with vapors of TiCl₄ and H₂O at 200°C is investigated. The influence of the number of synthesis cycles on the character of the buildup of the surface titanium oxide structures and changes in the adsorption and structural characteristics of modified silica is shown.     

Urease-mediated room-temperature synthesis of nanocrystalline titanium dioxide

Enzymes are an important class of biological molecules whose specific functionalities can be exploited to perform tasks beyond the reach of conventional chemistry. Because they are operational under environmentally friendly, ambient conditions, the adaptation of these biomacromolecules can potentially be used to replace current energy-intensive and environmentally harsh synthesis methods for materials. Here we used a hydrolytic enzyme, urease, to modify the solution environment around a water-soluble and stable TiO(2) precursor to synthesize nanocrystalline titanium dioxide under environmentally benign conditions. This urease-mediated synthesis yields nearly monodisperse TiO(2) nanostructures with high surface area that can be utilized for numerous energy-based applications such as low-cost photovoltaics and photocatalysts.     

Redox-controlled photosensitization of nanocrystalline titanium dioxide.

Photosensitization of nanocrystalline titanium dioxide materials has been achieved by chemisorption of the pentacyanothiamineferrate(II) complex, which offers a relatively high redox potential that determines the photoelectrochemical properties of the photosensitized TiO(2). The adsorbed pentacyanoferrate complex binds to TiO(2) through the cyanide bridge and forms a new surface complex characterized by a metal-to-metal charge-transfer transition (MMCT) (Fe(II)-->Ti(IV)). The photosensitization can be observed only at low potentials at which Fe(II) moieties are present. Photocurrent switching between anodic and cathodic can be induced by varying either the photoelectrode potential or the wavelength of the incident light. Simple molecular modeling-together with spectroscopic and electrochemical measurements-allows the elucidation of the mechanism of the observed photoelectrochemical behavior.     

Adsorption-driven photocatalytic activity of mesoporous titanium dioxide

Titanium dioxide with a mesoporous structure, when photoactivated in water, demonstrates an unprecedented photocatalytic activity, driven strongly by an adsorption degree of molecules onto the catalyst surface, which promotes a preferential conversion of a well-adsorbed molecule. This catalyzes a selective transformation of a well-adsorbed molecule into a less-adsorbed molecule, so-labeled "stick-and-leave" transformation, which promotes a direct hydroxylation of benzene to phenol, one of the most difficult synthetic reactions, with very high selectivity (>80%) and using water as a source of oxidant.     

二氧化钛介孔分子筛的合成和表征

以高嵌段共聚物为模板剂在中性条件下制备二氧化钛介孔分子筛,并以TG-DTA,XRD,TEM和N~2吸附方法对脱除模板剂后的样品进行了表征。实验结果表明,该介孔分子筛具有较高的比表面,以及六方堆积的均匀孔道,焙烧过程中孔壁可部分晶化成锐钛矿型TiO~2的小晶粒。在分子筛孔壁中引入稀土元素可提高介孔结构稳定性。     

Low temperature deposition of nanocrystalline titanium dioxide from titanium tetraisopropoxide

Effect of ozone and water vapor on the chemical deposition of TiO₂ from the gas phase in the system of titanium tetraisopropylate-oxygen was examined. Introduction of ozone in the reaction medium was shown to result in the precipitation of smooth TiO₂ layers at 240°C, and the addition of water vapor leads to the formation with higher rate of unconsolidated layers. Adding ozone to the reaction medium with low moisture content (up to 0.65 Pa) allows obtaining at temperatures 250–350°C with high rate of growth the TiO₂ layers with the anatase nanocrystals of high photocatalytic activity.     

High-performance titanium dioxide photocatalyst on ordered mesoporous carbon support

Anatase TiO₂ photocatalysts supported with the ordered mesoporous carbon, CMK-3, were synthesized by the incorporation of TiO₂ into CMK-3 followed by heating at 700 °C. The structural properties of the TiO₂ on CMK-3 were investigated by X-ray diffraction, nitrogen physisorption and electron microscopy techniques. In particular, TiO₂ was observed both inside and the external surface of CMK-3. The photocatalytic activity of TiO₂ on CMK-3 under UV-light exhibited higher efficiency in removing the Rhodamine 6G dye solution than the commercial photocatalyst P25 and TiO₂ on activated carbon. It was attributed to the synergistic effect of large surface area adsorption provided by mesoporous CMK-3 and the distinctive location of TiO₂ on the external surface of CMK-3.     

Sonochemical fabrication of fluorinated mesoporous titanium dioxide microspheres

A sonochemical-hydrothermal method for preparing fluorinated mesoporous TiO₂ microspheres was developed. Formation of mesoporous TiO₂ and doping of fluorine was achieved by sonication and then hydrothermal treatment of a solution containing titanium isopropoxide, template, and sodium fluoride. The as-synthesized TiO₂ microspheres were characterized by X-ray diffraction (XRD), Fourier translation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, photoluminescence spectroscopy (PL), and BET surface areas. The P123 template was removed completely during the hydrothermal and washing steps, which was different from the conventional calcination treatment. The as- synthesized TiO₂ microspheres had good crystallinity and high stability. Results from the photocatalytic degradation of methylene blue (MB) showed that fluorination could remarkably improve the photocatalytic activity of titanium dioxide.     

Synthesis of self-standing mesoporous nanocrystalline titania-phosphorus oxide composite films

Self-standing, transparent, thick (approximately 90 microm) mesoporous titania-phosphorus oxide composite films containing anatase nanocrystallites were synthesized using the evaporation-induced co-assembly of an amphiphilic triblock copolymer template, titanium tetraethoxide, and phosphorus chloride.     

Doped titanium dioxide nanocrystalline powders with high photocatalytic activity

Doped titanium dioxide nanopowders (M:TiO₂; M=Fe, Co, Nb, Sb) with anatase structure were successfully synthesized through an hydrothermal route preceded by a precipitation doping step. Structural and morphological characterizations were performed by powder XRD and TEM. Thermodynamic stability studies allowed to conclude that the anatase structure is highly stable for all doped TiO₂ prepared compounds. The photocatalytic efficiency of the synthesized nanopowders was tested and the results showed an appreciable enhancement in the photoactivity of the Sb:TiO₂ and Nb:TiO₂, whereas no photocatalytic activity was detected for the Fe:TiO₂ and Co:TiO₂ nanopowders. These results were correlated to the doping ions oxidation states, determined by Mössbauer spectroscopy and magnetization data.     

Synthesis of thermally stable mesoporous cerium oxide with nanocrystalline frameworks using mesoporous silica templates

Highly ordered mesoporous cerium oxides, composed of nanocrystalline pore walls and exhibiting high thermal stability even at 973 K, were synthesized using mesoporous silica templates with hexagonal p6mm and cubic Ia3d symmetries.     

Hard templating of nanocrystalline titanium dioxide with chiral nematic ordering

Anatase TiO(2) nanocrystals have been organized into high-surface-area (150-230 m(2) g(-1)) mesoporous films with long-range chiral nematic ordering. The chiral structure of the anatase films causes them to selectively reflect circularly polarized light and appear iridescent. These materials show replication of structural features found in the silica template on nanometer to millimeter length scales.     

介孔TiO2粉体的合成和表征及光催化性能研究

本文以甘油为结构导向剂,运用水热合成法制备了介孔二氧化钛粉体(MT),采用抽提和焙烧两种方法除去结构导向剂.分别对合成的样品、P25和商品TiO2粉末(PT)进行了XRD、TEM、TGA、N2等温吸附-脱附等实验表征,根据TGA计算了样品的表面羟基密度.研究了样品光催化降解甲基橙效率与其表面性质的关系.结果表明,经焙烧除去结构导向剂的样品的比表面最高,达285.3m2·g-1,孔径4nm～6nm,具有良好的光催化降解甲基橙性能.     

Effect of yttrium oxide on the formation of the phase composition and porous structure of titanium dioxide

The formation of the structure of TiO₂ (anatase) doped with 1–5 mol % Y₂O₃ is reported. The dopant changes the anatase structure from regular to nanocrystalline. The nanocruystalline structure consists of incoherently intergrown 5- to 7-nm anatase crystallites (500°C) separated by interblock boundaries accommodating yttrium ions. The formation of the nanocrystalline anatase structure stabilizes small anatase crystallites and raises the anatase-to-rutile phase transition temperature above 900°C. Owing to this structure, the developed specific surface area and fine porous texture of yttrium oxide-doped titanium dioxide survive up to higher temperatures than those of undoped titanium dioxide.     

A nitric oxide biosensor based on the photovoltaic effect of nano titanium dioxide on hemoglobin

A nitric oxide biosensor based on the photovoltaic effect of nano titanium dioxide on hemoglobin was fabricated with high sensitivity, selectivity, as well as stability. The linear detection concentration range was 5.0 × 10⁻⁶–4.0 × 10⁻⁴ M. The detection limit was 1.0 × 10⁻⁶ M with a sensitivity of 8 nA/μM. The possible coexisting compounds would not interfere with the nitric oxide detection. The article is published in the original.     

Synthesis,structure, and photocatalytic properties of titanium(IV) oxide modified with silver oxide nanoparticles on a boron-containing mesoporous support

A method for the synthesis of TiO₂–B₂O₃–Ag composite has been proposed. The composite structure and phase composition have been determined by X-ray diffraction analysis, IR spectroscopy, and scanning as well as transmission electron microscopy. The introduction of boron oxide in the TiO₂–Ag composite enhances catalytic activity of the samples in the reactions of methyl orange photodecomposition.     

The instructive redox behaviour of 4‐ferrocenylcatechol on nanocrystalline titanium dioxide electrodes

An investigation into the redox behaviour of 4‐ferrocenylcatechol bound to nanocrystalline TiO₂ electrodes identified a limitation to the use of catechol as an electron‐transfer facilitating anchoring group. 4‐Ferrocenylcatechol was adsorbed to transparent nanocrystalline TiO₂ electrodes. UV–visible spectra of the modified electrode were recorded in an acetonitrile‐electrolyte solution. At an applied potential of + 0.45 mV (vs Ag/AgCl/Cl^?) the ferrocenyl group oxidized to the ferrocenium cation and the catecholate group oxidized to the benzoquinone form. Subsequent application of a potential of 0 V reduced the ferrocenium to ferrocene but, owing to the irreversibility of the catechol oxidation in aprotic solvents, benzoquinone is not reduced to catecholate and subsequently desorbs and is lost due into solution. Electrochromic switching of the ferrocenyl electrochromophore on TiO₂ with aprotic electrolyte is, therefore, irreversible. Copyright © 2006 John Wiley & Sons, Ltd.