Influence of morphology and composition of fumed oxides on changes in their structural and adsorptive characteristics on hydrothermal treatment in steam phase at different temperatures

A series of fumed oxides such as silica, titania, alumina, silica/alumina (SA), silica/titania (ST), and alumina/silica/titania (AST), initial and hydrothermally treated (HTT) in the steam phase at T(HTT)=150, 250, and 350 degrees C was studied by adsorption, AFM, XRD, FTIR, and theoretical methods. Diminution of the size of primary particles (corresponding to increasing S(BET)) of initial silica and mixed oxides results in enhancement of their structural changes on HTT with elevating T(HTT) and increasing density of packing of primary particles in the secondary structures. Relative changes in the texture of treated fumed silicas are smaller than those of mesoporous silica gels occurring under similar HTT conditions. On HTT, aggregates of primary particles and their agglomerates become denser but their surface layers become looser because of transfer of silica fragments from one particle to another, and the smaller the initial primary particles, the greater the relative diminution of the specific surface area S(BET) for the same type of primary particle packing in aggregates. Relative changes in the pore volume V(p) (or V(BJHd)) on HTT are more complex than that of S(BET), as for many samples the V(p) value increases especially at T(HTT)=150 degrees C. Alumina and titania partially inhibit structural changes on HTT, which decrease in the series silica > SA > AST approximately ST.     

Surface electric and titration behaviour of fumed oxides

Adsorption of Pb(II), Sr(II), and Cs(I) on fumed silica, alumina, titania, silica/titania (ST), silica/alumina (SA), and alumina/silica/titania (AST) reveals that mixed oxides containing titania have a greater adsorptive capability in respect to metal cations than individual and SA oxides. Pyrocarbon deposits on fumed oxides enhance the adsorption of metal ions. Calculations of electrophoretic potential (ζ) with consideration for the porosity of aggregates of primary particles of AST show a significant influence of surface alumina (at pH<8) and titania and silica (at pH>8) on the ζ values. The effective diameter of particles (D_ef) of fumed oxides in aqueous media depends on pH for AST stronger than for ST (between isoelectric points (IEPs) of titania and alumina). A significant difference in the pH values of IEP and point of zero charge is observed for AST samples. A pyrocarbon influence on the ζ potential depends on the type of oxide matrix, since ζ increases for certain samples but for others it decreases. These changes depend nonlinearly on pH as well as the secondary particle size distributions (SPSDs) and D_ef.     

Heating effects on morphological and textural characteristics of individual and composite nanooxides

Morphological, structural and adsorption characteristics of nanooxides (fumed individual silica, alumina and titania, and composite silica/alumina, silica/titania and alumina/silica/titania) were compared after different treatments (wetting/drying, ball-milling, suspending/drying, heating) at different temperatures (373–1173 K) using low-temperature nitrogen adsorption data. The structural characteristics such as specific surface area (S _BET), pore volume (V _p), pore (PSD) and particle (PaSD) size distributions (calculated using self-consisting regularization procedure with respect to both PSD and PaSD), fractality, adsorption energy distributions depend differently on heating temperature because desorption of water molecularly and dissociatively adsorbed at a surface and in bulk of primary nanoparticles occurs over a wide temperature range at different rates. These processes affect both structural and energetic characteristics of nanooxides.     

Experimental and modelization approach in the study of acid-site energy distribution by base desorption. Part I: modified silica surfaces

The acid properties of pure and modified silica surfaces were studied by 2-phenylethylamine (PEA) desorption in a thermogravimetric (TGA) apparatus, carrying out the experiments at different heating rates (5 < beta/(degrees C.min(-1)) < 30). The samples, containing about 13 wt % alumina, titania, and zirconia, were prepared by the sol-gel route from molecular precursors. The textural, structural, and surface properties of the materials were studied by complementary techniques (ICP, XRD, N(2) physisorption, SEM-EDS, and XPS). The chemical modification of the silica surface by enrichment with Al, Ti, or Zr, in amounts of about 90, 50, and 60% of that introduced in the preparation as determined by XPS, justified the increase of acidity of the modified silica surfaces compared with that of pure silica. The total number of strong acid sites was found to be in the order of SZ > SA > ST > S. Two different kinetic approaches were applied to the thermogravimetric data to kinetically interpret the PEA desorption from the different types of acid sites. The classical differential Kissinger model was found to be inadequate in representing the very complex situation of the acid surfaces. A more complex model is proposed by simultaneously taking into account PEA desorption from the different acid sites by a set of parallel and independent desorption reactions following Arrhenius's kinetic law. The fraction of each type of acid site on each surface and the relevant activation parameters were optimized through a computational procedure. Very good fitting of the experimental-calculated desorption profiles corroborated the validity of the model. For each surface, the acid-site energy distribution is presented and discussed in relationship to the surface composition of the oxides.     

Structural and adsorption characteristics and catalytic activity of titania and titania-containing nanomaterials

Morphological, structural, adsorption, and catalytic properties of highly disperse titania prepared using sulfate and pyrogenic methods, and fumed titania-containing mixed oxides, were studied using XRD, TG/DTA, nitrogen adsorption, (1)H NMR, FTIR, microcalorimetry on immersion of oxides in water and decane, thermally stimulated depolarization current (TSDC) and catalytic photodecomposition of methylene blue (MB). Phase composition and aggregation characteristics of nanoparticles (pore size distribution) of sulfate and pyrogenically prepared titania are very different; temperature dependent structural properties are thus very different. Catalytic activity for the photodecomposition of MB is greatest (per gram of TiO(2) for the pure oxide materials) for non-treated ultrafine titania PC-500, which has the largest S(BET) value and smallest particle size of the materials studied. However, this activity calculated per m(2) is higher for PC-105, possessing a much smaller S(BET) value than PC-500. The activity per unit surface area of titania is greatest for the fumed silica-titania mixed oxide ST20. Calcination of PC-500 at 650 degrees C leads to enhancement of anatase content and catalytic activity, but heating at 800 and 900 degrees C lowers the anatase content (since rutile appears) and diminishes catalytic activity, as well as the specific surface area because of nanoparticle sintering.     

Polydimethylsiloxane/silica/titania composites prepared by solvent-free sol–gel technique

Composites based on polydimethylsiloxane incorporating silica and titania were prepared by mixing polydimethylsiloxane with proper oxides precursors, tetraethyl-orthosilicate and tetrabutyl-orthotitanate. In the presence of environmental humidity and in acid catalysis, hydrolysis/condensation processes take place with formation of oxides and concomitantly polymer crosslinking. Partial replacement of SiO₂ in a polydimethylsiloxane/silica composite with titania (both generated in situ by sol–gel process) affects surface hydrophilicity (evaluated by dynamic contact angle), water vapor sorption ability (determined by dynamic vapor sorption) and thermal stability. The dielectric properties are also controlled by composition.     

High surface area sol–gel alumina–titania nanocatalyst

Alumina–titania mixed oxide nanocatalysts with molar ratios = 1:0.5, 1:1, 1:2, 1:5 have been synthesized by adopting a hybrid sol–gel route using boehmite sol as the precursor for alumina and titanium isopropoxide as the precursor for titania. The thermal properties, XRD phase analysis, specific surface area, adsorption isotherms and pore size details along with temperature programmed desorption of ammonia are presented. A specific surface area as high as 291 m²/g is observed for 1:5 Al₂O₃/TiO₂ composition calcined at 400 °C, but the same composition when calcined at 1,000 °C, resulted in a surface area of 4 m²/g, while 1:0.5 composition shows a specific surface area of 41 m²/g at 1,000 °C. Temperature programmed desorption (of ammonia) results show more acidic nature for the titania rich mixed oxide compositions. Transmission electron microscopy of low and high titania content samples calcined at 400 °C, shows homogeneous distribution of phases in the nano range. In the mixed oxide, the particle size ranges between 10–20 nm depending on titania content. The detailed porosity data analysis contributes very much in designing alumina–titania mixed oxide nanocatalysts.     

Effects of Ti Addition on Alumina/Titania Composite Aerogels Synthesized by Sol–Gel Process and Supercritical Ethanol Drying

Alumina/titania composite aerogels with different titania contents were synthesized by the sol–gel process and supercritical ethanol drying. The structures and morphologies of synthesized aerogels were analyzed by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetry, and N₂ adsorption–desorption tests. Supercritical ethanol drying induced the crystallization of titania, which prompted the transformation of the structure from pseudoboehmite to γ‐Al₂O₃ . Reversely, alumina retarded the anatase‐to‐rutile transformation of titania. The content of titania significantly affected the structure and morphology of alumina/titania composite aerogels. A high content of titania (≥40%) resulted in the phase separation of titania particles, which grew to form the anatase phase octahedral particles with well‐developed facets. When the titania content was low, titania particles could be homogeneously dispersed in alumina particles to form spherical clusters with the poor crystallinity. Titania particles were in the anatase phase, and no rutile phase was formed until the temperature rose to 1000°C. In addition, titania addition resulted in a decrease in the specific surface area (SSA) of alumina aerogels because the SSA of titania was lower than that of alumina aerogels.     

碳/氧化物复合物中碳层对氧化物相变的影响

碳/氧化铝(氧化钛)复合物具有独特的物理化学性质,在吸附和催化过程中有广泛应用.复合物中碳层对氧化物的相变有重要影响.在高温下通氧气焙烧碳/γ-Al2O3复合物可使γ-Al2O3迅速转变为α-Al2O3;而在惰性气氛中,碳层可显著抑制氧化铝的相变与烧结.碳/氧化钛体系中,碳层可明显提高氧化钛在惰性气氛中的热稳定性,在800℃以下碳层能有效阻止锐钛矿相向金红石相的转变;在含氧气氛中控制焙烧条件可将碳层完全除去而基本不影响氧化钛的物相组成及织构.因此,碳层可作为一种特殊的表面修饰剂,既可在高温下抑制氧化物的相变,又可避免在氧化物中引入掺杂元素.     

Characterization of Fumed Alumina/Silica/Titania in the Gas Phase and in Aqueous Suspension

Fumed oxide alumina/silica/titania was studied in comparison with fumed alumina, silica, titania, alumina/silica, and titania/silica by means of XRD, ¹H NMR, IR, optical, dielectric relaxation, and photon correlation spectroscopies, electrophoresis, and quantum chemical methods. The explored Al₂O₃/SiO₂/TiO₂ consists of amorphous alumina (22 wt%), amorphous silica (28 wt%), and crystalline titania (50 wt%, with a blend of anatase (88%) and rutile (12%)) and has a wide assortment of Brønsted and Lewis acid sites, which provide a greater acidity than that of individual fumed alumina, silica, or titania and an acidity close to that of fumed alumina/silica or titania/silica. The changes in the Gibbs free energy (ΔG) of interfacial water in an aqueous suspension of Al₂O₃/SiO₂/TiO₂ are close to the ΔG values of the dispersions of pure rutile but markedly lower than those of alumina, anatase, or rutile covered by alumina and silica. The zeta potential of Al₂O₃/SiO₂/TiO₂ (pH of the isoelectric point (IEP) equals ≈3.3) is akin to that of fumed titania (pH(IEP_TiO2) ≈ 6) at pH > 6, but it significantly differs from the ζ of fumed alumina (pH(IEP_Al2O3) ≈ 9.8) at any pH value as well as those of fumed silica, titania/silica, and alumina/silica at pH < 6. The particle size distribution in the diluted aqueous suspensions of Al₂O₃/SiO₂/TiO₂ studied by means of photon correlation spectroscopy depends relatively slightly on pH in contrast to the titania/silica or alumina/silica dispersions. Theoretical calculations of oxide cluster interaction with water show a high probability of hydrolysis of Al–O–Ti and Si–O–Ti bonds strained at the interface of alumina/titania or silica/titania due to structural differences in the lattices of the corresponding individual oxides. Ab initio calculated chemical shift δ_H values of H atoms in different hydroxyl groups at the oxide clusters and in bound water molecules are in agreement with the ¹H NMR data and show a significant impact of charged particles (H₃O⁺ or OH⁻) on the average δ_H values of water droplets with (H₂O)_n at n between 2 and 48.     

Highly Dispersed X/SiO(2) and C/X/SiO(2) (X=Alumina, Titania, Alumina/Titania) in the Gas and Liquid Media

Fumed oxides, such as silica, alumina, titania, and mixed X/silicas (X=Al₂O₃ (AS), TiO₂ (TS), CVD-TiO₂, Al₂O₃/TiO₂ (AST)), pristine or covered by carbon deposits formed due to pyrolysis of cyclohexene, were studied using nitrogen adsorption–desorption, photon correlation spectroscopy particle sizing, and electrophoresis. A significant influence of the nature of surface-active sites and structural features of oxides (individual silica, mixed fumed, or prepared using chemical vapor deposition (CVD)) on the pyrolysis of cyclohexene is observed with respect to the pore size distributions due to differences between primary particles in aggregates and on their outer surfaces in the filling of channels by pyrocarbon, resulting also in a decrease in fractal dimension. Structural characteristics and dependences of the particle size distribution and electrokinetic potential of X/SiO₂ and C/X/SiO₂ on the pH of aqueous suspensions suggest that the carbon deposit covers mainly acidic sites at the X/SiO₂ interfaces and X phase patches possessing catalytic activity in pyrolysis, as the negative charge of particles is reduced by pyrocarbon grafting.     

Superhydrofobic effect of hybrid organo-inorganic materials

Superhydrophobic films were obtained on the basis of sol–gel-derived titania or alumina/dodecylamine hybrid materials. It has been shown that wettability of surfaces of the inorganic oxides changes from superhydrophilic to superhydrophobic. For superhydrophobic materials, the surface roughness of the hybrid films on the basis of titania and alumina is 39 and 55 μm, respectively, and water contact angle is about 150°.     

Retention of β blockers on native titania stationary phase

In recent years, metal oxides such as titania have been commercially available as chromatographic beds that can potentially be used to achieve novel separations of polar compounds. For example β blockers, which are more often encountered in environmental sciences, have a wide range of polarity, and their basic character leads to difficult sample treatment and separation on conventional silica‐based sorbents. The contribution of titania to the selective analysis of nine β blockers was evaluated in terms of retention mechanisms observed in hydrophilic interaction LC using acetonitrile/water mobile phases with various additives. The mobile phase additives enabled to control the β blocker charge as well as the titania surface charge. Depending on their respective ionic state, various retention mechanisms were identified at low water contents (<40%), including mainly adsorption mixed with hydrophilic interaction LC partition, ion exchange and ion exclusion. An unexpected retention was also observed for high water content and high pH, changing the selectivity of the support.     

Structural and Energetic Nonuniformities of Pyrocarbon-Mineral Adsorbents

Several series of pyrocarbon-mineral adsorbents (carbosils) were studied using the nitrogen adsorption method to compute structural and energetic parameters within the scope of overall adsorption isotherm approximation applying a regularization procedure with consideration for surface heterogeneity. A portion of pyrocarbon deposits (graphene clusters) fills mesopores of the oxide supports, but another portion represents relatively large nonporous pyrocarbon globules formed on the outer surfaces of the oxide matrices. Contributions of these two types of pyrocarbon deposits depend on the nature of oxide matrices and carbonized precursors. The characteristics of pyrocarbon formed on the silica (silica gel, fumed silica) surfaces differ from those for deposits prepared on the surfaces of titania/silica and alumina/silica or by the pyrolysis of metal acetylacetonates (Zr(AcAc)(4), TiO(AcAc)(2), Ni(AcAc)(2), Zn(AcAc)(2), Cr(AcAc)(3), Co(AcAc)(2)) on mesoporous silica gel. The structural and energetic characteristics estimated using the adsorption method with consideration for the adsorbent heterogeneity are fruitful for comparative analysis of the (1)H NMR spectra of water adsorbed on carbosils from the gas phase or unfrozen in the aqueous suspensions at T < 273 K. Copyright 2001 Academic Press.     

The Preparation and Properties of Titanium Dioxide Pigments with Acidic Surfaces

Titanium dioxide pigments used in commercial polymers are generally coated with a neutral, alumina/silica gel-coat to improve the pigment physical properties and also to reduce the chemical activity of the titania surface. Production of an acidic alumina/silica coating on titania pigments gives them a chemical activity similar to that previously found in dry clays. This activity is sufficient to increase greatly the bonding of basic organic materials to the pigment surfaces. The enhanced bonding can lead to materials with highly organophilic surfaces. The property changes in polymer composites brought about by these acidic pigments are discussed.     

Adsorption of Dihydrogen on Mesoporous Materials at 77 K

The adsorption of dihydrogen at 77 K is studied on a series of oxide materials including silica, pure titania and alumina, and mixed oxides. The experimental data obtained suggest that the sorption properties per unit area of mesopore surface depend on both the texture and chemical composition of the sample. A comparative procedure for the analysis of dihydrogen adsorption isotherms is considered.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 642–647.Original Russian Text Copyright © 2005 by Gavrilov.     

Synthesis and characterization of new silica–titania mixed oxide in the presence of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide by sol–gel technique

Silica–titania mixed oxide were prepared by sol–gel method from tetraethylorthosilicate and titanium (IV) isopropoxide as precursors in the presence of room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [C₄MIm][NTf₂]. The effects of [C₄MIm][NTf₂] on the structural and textural characteristics of silica–titania matrix are investigated in this paper. The materials obtained were well characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis X-ray powder diffraction (XRPD), field emission scanning electron microscope (FESEM) and N₂ adsorption–desorption analysis. It is believed that the [C₄MIm][NTf₂] plays an important role as a template and the high surface area of the samples is thought to mainly attribute to the formation of microporous in the reaction. The synthesized materials showed the presence of C–N groups in the FTIR spectrum which indicates the presence of RTIL in the silica–titania matrix. XRPD, FESEM and N₂ adsorption–desorption analysis results indicated that the composite materials possessed good microporous character. The subsequent material displayed average pore diameter of 1.70–2.12 nm, pore volume of 0.08–0.19 cm³/g and BET surface area of 191–386 m²/g. Increasing the content of RTIL resulted in an increase of the average pore diameter of the silica–titania gel.     

Investigation of the porosity of silica and alumina with chemically bonded polystyrene

The effect of modification of porous silica and alumina with a copolymer of styrene and vinylsilane on the porosity of oxides have been investigated by means of low temperature nitrogen sorption. Only small changes of the specific surface area and of the specific pore volume were observed on modification of oxides with non-cross-linked copolymer. The specific surface area significantly increased after the cross-linking of the deposited polymeric layer while the specific pore volume remains almost unaffected. A broad hysteresis loop appears in the nitrogen sorption isotherm for the alumina modified with the cross-linked polymer. The porosity of oxides modified by chemisorption method differed strongly from that observed for composites modified by physisorption of polymer.     

Spectroscopic and structural characterization of chlorine loading effects on Mo/Si:Ti catalysts in oxidative dehydrogenation of ethane

The structural changes induced in a silica-titania mixed-oxide support (1:1 molar ratio) by chlorine addition at different loading levels, their relation to the structural characteristics of supported MoOx species over the support, and their correlation with ethane oxidative dehydrogenation (ODH) activity have been examined. The molybdenum and chlorine precursors are incorporated into the Si/Ti support network as it forms during gelation by using a "one-pot" modified sol-gel/coprecipitation technique. In situ X-ray diffraction during calcination shows the Si/Ti 1:1 mixed-oxide support is in a state of nanodispersed anatase titania over amorphous silica. With the addition of molybdenum and chlorine modifier, this anatase feature becomes more pronounced, indicating a decreased dispersion of titania. The effective titania surface area on the chlorine-doped Si:Ti support obtained from 2-propanol temperature-programmed reaction supports this observation. Raman spectra of dehydrated samples point to an enhanced interaction of MoOx species with silica at the expense of titania. X-ray photoelectron spectroscopic results show that, without forming a molybdenum chloride, the presence of chlorine significantly alters the relative surface concentration of Si vs Ti, the electronic structure of the surface MoOx species, and the oxygen environment around supported MoOx species in the Si/Ti network. Secondary ion mass spectrometry detected the existence of SiCl fragments from the mass spectra, which provides molecular insight into the location of chlorine in Mo/Si:Ti catalysts. The observed increase in ethane ODH selectivity with chlorine modification may be ascribed to the MoOx species sharing more complex ligands with silica and titania with the indirect participation of chlorine. Steady-state isotopic transient kinetic analysis (SSITKA) is used to to examine the oxygen insertion and exchange mechanisms. The catalysts show very little oxygen exchange with the gas phase in the absence of a reaction medium. During the steady-state ODH reaction, lattice oxygen appears to be the primary source of oxygen in the formation of water and CO2.     

Physical–chemical and catalytic properties of deposited MoO3 and V2O5

The deposition of molybdenum and vanadium oxides onto fumed silica, titania, and alumina as supports through dry milling has been carried out. The structure of prepared compositions has been investigated by means of XRD, DTA?CTG, FTIR, and UV?CVis spectroscopy, nitrogen adsorption. The deposited crystal phases are sufficiently uniformly distributed on support surface. The supported oxides are subjected to dispersion in process of milling to the state of oligomeric or isolated species. Milled bulk and deposited MoO₃ (first of all, on alumina) possesses improved catalytic performance in process of epoxidation of 1-octene. Vanadium pentoxide also has higher activity in this process.