Jiri Rathousky

Ultrasmall Titania Nanocrystals and Their Direct Assembly into Mesoporous Structures Showing Fast Lithium Insertion

Ultrasmall and highly soluble anatase nanoparticles were synthesized from TiCl(4) using tert-butyl alcohol as a new reaction medium. This synthetic protocol widens the scope of nonaqueous sol-gel methods to TiO(2) nanoparticles of around 3 nm with excellent dispersibility in ethanol and tert-butanol. Microwave heating was found to enhance the crystallinity of the nanoparticles and to drastically shorten the reaction time to less than 1 h at temperatures as low as 50 degrees C. The extremely small size of the nanoparticles and their dispersibility make it possible to use commercial Pluronic surfactants for evaporation-induced self-assembly of the nanoparticulate building blocks into periodic mesoporous structures. A solution of particles after synthesis can be directly used for preparation of mesoporous films without the need for particle separation. The mesoporous titania coatings fabricated using this one-pot procedure are crystalline and exhibit high surface areas of up to 300 m(2)/g. The advantages of the retention of the mesoporous order with extremely thin nanocrystalline walls were shown by electrochemical lithium insertion. The films made using microwave-treated nanoparticles showed supercapacitive behavior with high maximum capacitance due to quantitative lithiation with a 10-fold increase of charging rates compared to a standard reference electrode made from 20 nm anatase particles.

Niobium-Doped Titania Nanoparticles: Synthesis and Assembly into Mesoporous Films and Electrical Conductivity

Crystalline niobium-doped titania nanoparticles were synthesized via solvothermal procedures using tert-butyl alcohol as a novel reaction medium, and their assembly into mesoporous films was investigated. The solvothermal procedure enables the preparation of crystalline doped and undoped nonagglomerated titania nanoparticles, whose size can be controlled from 4 to 15 nm by changing the reaction temperature and time. The anatase lattice of these particles can incorporate more than 20 mol % of Nb ions. The nanoparticles can be easily dispersed at high concentrations in THF to form stable colloidal suspensions and can be assembled into uniform porous mesostructures directed by the commercial Pluronic block copolymer F127. The resulting mesoporous films show a regular mesostructure with a d spacing of about 17 nm, a uniform pore size of about 10 nm with crystalline walls, a high porosity of 43%, and a large surface area of 190 m(2) cm(-3). Substitutional doping with niobium ions drastically increases the electrical conductivity of the titania particles. The electrical conductivity of as-prepared nanoparticles containing 20 mol % of Nb is 2 x 10(-5) S cm(-1); it increases to 0.25 S cm(-1) after treatment at 600 °C in nitrogen.

Mesoporous thin film TiO2 electrodes

Thin layer electrodes (200–500 nm) of highly organized nanotextured anatase were prepared by hydrolysis of TiCl4 in the presence of poly(alkylene oxide) block copolymer, Pluronic P-123, acting as a structure-directing agent. Electrochemical insertion of Li was studied in LiN(CF3SO2)2 + ethylene carbonate + dimethoxyethane. Cyclic voltammograms of these electrodes showed unusual occurrence of two pairs of cathodic/anodic peaks at 1.5 and 1.6 V vs. Li/Li+. These peaks can serve as indicators of structural perfection of the mesoscopic skeleton; they diminish after mechanical or thermal destruction of the organized nanotexture.

Formation of CdS nanoparticles within functionalized siliceous MCM-41

Cadmium sulfide nanoparticles were prepared within the siliceous MCM-41 mesoporous molecular sieve, whose surface was functionalized with 3-mercaptopropyltrimethoxysilane at different temperatures. Their size, estimated from diffuse reflectance UV/VIS spectra, decreases with increasing number of introduced thiol groups acting as anchors.

New mesoporous titanosilicate molecular sieve

New mesoporous titanium containing molecular sieves were prepared on the basis of the liquid-crystal templating mechanism originally used for the synthesis of MCM-41 materials. The structure characteristics of titanosilicate sieves with lower content of titanium are very similar to those of aluminosilicate MCM-41 from which it follows that titanium is built in pore walls. If the concentration of the titanium component in the reaction mixture at the beginning of the synthesis is too high an extra-wall titanium oxide species forms; the structure of thus prepared sieves is similar to that of silicate MCM-41.

Low-Temperature Preparation of Crystalline Nanoporous TiO2 Films by Surfactant-Assisted Anodic Electrodeposition

Highly porous, fully crystalline TiO 2 films were prepared without high-temperature treatment by cathodic electrodeposition using the surfactant sodium dodecyl sulfate as a structure-directing agent. X-ray diffraction and transmission electron microscopy show the almost exclusive presence of rutile in the films. Calcination in air leads to substantial texture changes, namely grain coarsening, the removal of micropores, and the creation of a large amount of mesopores, leading to higher efficiency of the calcined films in dye-sensitized solar cells compared to as-deposited films.

Enhancement of Activity and Selectivity in Acid‐Catalyzed Reactions by Dealuminated Hierarchical Zeolites

High-silica zeolites with crystalline aluminosilicate frameworks balance the charge of strongly acidic protons during the processing of oil, in petrochemistry, and increasingly in numerous organic syntheses. The transformation of hydrocarbons is controlled by the concentration and strength of the acid sites and the dimensions and architecture of the inner pores. Zeolite micropores, which have a diameter similar to organic molecules, govern the shape selectivity of the reaction in the inner space, but also result in slow transport of reactants and products, thus limiting the reaction rate. Several approaches have been developed to enhance the mass transport by using zeolite nanosheets and nanocrystals, or zeolites that contain both microand mesopores. The latter hierarchical zeolites were prepared by confined crystal growth, by using polymers as mesoporogens, or through post-synthesis desilication or dealumination processes. The advantage of the presence of mesopores is, however, accompanied by the nonshape-selective environment of the acid sites located in the mesopores. Our interest in the effective formation of secondary mesoporosity through postsynthesis alkaline treatment of conventional zeolites prompted us to study the potential of leaching procedures for the preparation of hierarchical zeolites, preserving the shape-selective environment of the active sites. The main principles of forming mesopores in high-silica zeolites through alkaline leaching have been described by Groen et al. They demonstrated that dissolution of Si depends mainly on the Al concentration in the framework and occurs in the Si-rich areas. Al atoms partly remain at the framework sites and partly form extra-framework Al species in the mesopores. Groen et al. 13] and Caicedo-Realpe and PerezRamirez have shown that the formed Al species can be removed by treatment with mild acid, thus restoring the original Si/Al ratio. This treatment increased the isomerization of o-xylene, however, the selectivity for p-xylene did not reach that of parent microporous zeolites. This study is primarily concerned with the elimination of both the extraframework and framework Al species, and thus the related acid sites from the mesopores of the desilicated zeolites by employing oxalic acid. The advantage of hierarchical zeolites with acid sites predominantly located in the confined reaction space of the micropores is demonstrated on acid-catalyzed reactions controlled by shape-selectivity effects. TEM images of the alkalineand subsequently acidleached zeolites are given in Figure 1. They clearly show that the treatment resulted in the extensive formation of a secondary mesoporous structure, which is characterized by numerous crystal cavities, which are more populated in ZSM-5 (Si/ Al = 22.2) compared to mordenite (MOR, Si/Al = 12.1). The adsorption isotherms of treated ZSM-5 zeolites (Figure 2) indicate adsorption in the zeolite micropores and an H3 hysteresis loop typical for slit-shaped mesopores. But the extensive formation of a mesoporous structure also resulted in a decrease in the micropore volume. Treatment with oxalic acid further extended the mesopore volume and the micropore volume increased, with the final value only slightly lower compared to the parent zeolite. Al plugs, which were formed in the mesopores after desilication and blocked parts of the micropores, were removed by acid leaching, similar to results of Caicedo-Realpe and Perez-Ramirez. With mordenite, alkaline and acid leaching resulted in similar textural changes and led to well-developed secondary mesoporosity with preserved high micropore volumes. The dealuminated zeolite surface was analyzed by XPS monitoring of the relative concentration of Al to Si in the zeolite (sub)surface layers ( 50 ) by the Al 2p and Si 2p electron levels. The surface Si/Al ratio of both desilicated ZSM-5 and mordenite zeolites compared to the bulk composition (Table 1) indicated accumulation of Al species on the external crystal surface. In contrast, zeolites treated with oxalic acid resulted in a slight surface enrichment in Si. Analysis of the Brønsted and Lewis acid sites of dealuminated micro-mesoporous zeolites indicated predominant Brønsted acidity corresponding to the concentration of Al in the framework (Table 1). The population of acid sites in the dealuminated micro-mesoporous (deAlmm) ZSM-5(I) was analyzed using the FTIR spectra of adsorbed 2,6-ditertbutylpyridine (DTBPy), the kinetic diameter of which (10.5 ) does not allow it to penetrate into the [*] Dr. P. Sazama, Prof. Dr. Z. Sobalik, Dr. J. Dedecek, Dr. Z. Bastl, Dr. J. Rathousky, Dr. H. Jirglova J. Heyrovský Institute of Physical Chemistry Academy of Sciences of the Czech Republic 18223 Prague 8 (Czech Republic) E-mail: petr.sazama@jh-inst.cas.cz

Photocatalytic activity of porous multiwalled carbon nanotube-TiO2 composite layers for pollutant degradation.

TiO2 nanoparticles are suitable building blocks nanostructures for the synthesis of porous functional thin films. Here we report the preparation of films using brookite, P25 titania and anatase pristine nanoparticles and of nanocomposite layers combining anatase nanoparticles and multi-walled carbon nanotube (MWCNT) at various concentrations. The structure and phase composition of the layers were characterized by X-ray diffraction and Raman spectroscopy. Their morphology and texture properties were determined by scanning electron microscopy and krypton adsorption experiments, respectively. Additionally to a strong absorption in the UV range, the composites exhibited light absorption in the visible range as well. The photocatalytic performance of the layers was tested in the degradation of aqueous solutions of 4-chlorophenol serving as a model of an eco-persistent pollutant. Besides the determination of the decrease in the concentration of 4-chlorophenol, also the formation of intermediate degradation products, namely hydroquinone and benzoquinone, was followed. The presence of MWCNTs had a beneficial effect on the photocatalytic performance, a marked increase in the photocatalytic degradation rate constant being observed even at very low concentrations of MWCNTs. Compared to a P25 reference layer, the first order rate reaction constant increased by about 100% for the composite films containing MWCNTs at concentrations above 0.6 wt%. The key parameters for the enhancement of the photocatalytic performance are discussed. The presence of carbon nanotubes influences beneficially the degradation of 4-chlorophenol by an attack of the primarily photoproduced hydroxyl radicals onto the 4-chlorophenol molecules. The degradation due to the direct charge transfer is practically not influenced at all.

Multilayered ordered mesoporous platinum/titania composite films: does the photocatalytic activity benefit from the film thickness?

Multilayered films of TiO2 with ordered cubic mesoporosity were grown via layer-by-layer deposition on a conductive FTO (F-doped SnO2) substrate by dip-coating and subsequent calcination at 400 °C. Since platinum nanoparticles are known to enhance the photocatalytic activity, they were introduced into the TiO2 mesopores by pulsed electrodeposition. Additionally, sandwich-like layers with up to five alternating TiO2 and Pt layers were prepared. The photocatalytic gas-phase oxidation of acetaldehyde served as a test reaction to characterize the activity in the gas phase of both pristine TiO2 as well as Pt/TiO2 single- and multilayer films. The ordered mesoporous pristine TiO2 and Pt/TiO2 nanocomposites exhibited significantly higher photoactivity than commercial Pilkington Activ™ glass and dense TiO2 films. Moreover for pristine TiO2 films, those consisting of three layers (about 650 nm in thickness), were shown to be sufficient to achieve a maximum photonic efficiency of ζ = 0.45%. For the Pt/TiO2 system, however, a single-layer film with a total thickness of only about 220 nm exhibited an almost identical activity. Moreover, repetitive experiments demonstrated that the newly prepared photocatalyst films did not suffer from a decrease in the photocatalytic activity, evincing their potential for practical applications.

Adsorption and photocatalytic and photosensitised bleaching of acid orange 7 on multilayer mesoporous films of TiO2

A series of mesoporous films of titania of different thicknesses are prepared and their surface areas and porosities determined by physical adsorption using Kr as the adsorbate. The amounts of acid orange 7 (AO7) adsorbed by these films are found to be proportional to their measured surface areas and so the possibility of using this as a method of determining the surface area of thin titania films is discussed. The initial rates of UV-driven photocatalytic- and visible-driven photosensitised-bleaching of AO7 in solution, upon UVA and visible light irradiation, respectively, are also directly dependent upon the measured surface areas of the titania films. The quantum efficiencies for the UV photocatalytic- and visible photosensitised-bleaching of AO7 by the thickest of the AO7 films were estimated to be 0.08 and 0.01%, respectively.