Synthesis and colloidochemical properties of cerium dioxide hydrosols stabilized by zirconium polycationic compounds

It is shown that cerium dioxide hydrosols can be stabilized by polycationic compounds of zirconium, and the optimum conditions of the stabilization are determined. Stable CeO₂ hydrosols with concentrations of higher than 20 wt % are prepared; the sizes and electrophoretic mobility of their particles, as well as sol stability in the presence of some electrolytes, are investigated. The nature of the aggregation stability of the stabilized cerium dioxide sols is discussed.     

Degradation of parathion methyl by reactive sorption on the cerium oxide surface: The effect of solvent on the degradation efficiency

A simple and easily scalable “wet” procedure was used to prepare nanocrystalline cerium oxide capable of destroying the toxic organophosphate pesticide parathion methyl. The synthetic procedure consists of the direct precipitation of cerous salt with aqueous ammonia in the absence of CO₂. The prepared cerium oxide was able to decompose the organophosphate compounds both in nonpolar (e.g., heptane) and polar aprotic (e.g., acetonitrile) solvents. However, in solvents with hydrogen-bond donating ability, the –OH groups on the cerium oxide surface were solvated and inactivated. The preferential solvation model was used to express the experimental dependencies of the cerium oxide degradation efficiency on the composition of the water-acetonitrile mixture. In certain solvent systems, some empirical polarity scales, such as the alpha-scale or the Dimrodth-Richardt parameter ET(30), may be correlated with the degradation efficiency of cerium oxide.     

Determination of cerium(III) and cerium(IV) in nanodisperse ceria by chemical methods

Percentages of different valence cerium species have been determined in powdery samples, redispersible compositions, and aqueous sols of nanodisperse ceria prepared from cerium(IV) and cerium(III) salts by various methods with or without organic stabilizers. Cerium(III) is shown to be virtually absent in nearly all of the CeO₂ samples studied. Organic stabilizers are shown to be capable of reducing cerium(IV) in aqueous CeO₂ sols.     

Novel water based cerium acetate precursor solution for the deposition of epitaxial cerium oxide films as HTSC buffers

A novel water based precursor solution using ethylenediaminetetraacetic acid (H₄EDTA) as a complexant and acetic acid and ethylenediamine (EDA) as additional components to obtain CeO₂ buffer layers on Ni (5%W) tapes is described in detail. The influence of complexation behavior in the formation of transparent and homogenous sols and gels by the combination of cerium acetate, acetic acid and H₄EDTA has been studied. The optimal growth conditions for cerium oxide were Ar-5% H₂ gas processing atmosphere, solution concentration levels of 0.2–0.4 M, a dwell time of 60 min at 900 °C and 5–30 min at 1,050 °C. X-ray diffraction, SEM, spectroscopic ellipsometry and pole figures were used to characterize the CeO₂ films. Highly textured CeO₂ layers were obtained.     

Silica-Zirconia Sol–Gel Coatings Obtained by Different Synthesis Routes

Homogeneous xSiO₂-(1−x)ZrO₂ coatings have been prepared onto glass-slides, monocrystalline Si and stainless steel (AISI 304) using sols prepared via acid and basic catalysis. Zirconium tetrabutoxide (TBOZr), zirconium n-propoxide (TPZ), tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) were used as precursors of zirconia and silica, respectively. The different parameters involved in the synthesis procedure, as molar ratios H₂O/alkoxides, NaOH/alkoxides, and sintering temperature have been analysed, correlating the stability and rheological properties of the sols. The evolution and structure of the sols and coatings have been studied by FTIR. Coatings have been prepared by dipping from acid and basic sols. Electrophoretic Deposition (EPD) technique has also been used to prepare coatings onto stainless steel from basic particulate sols in order to increase the critical thickness. A maximum thickness of 0.5 μ m was reached by both dipping and EPD process for 75SiO₂: 25 ZrO₂ composition. The critical thickness decreases with ZrO₂ amount depending strongly of the drying conditions. Si–O–Zr bonds have been identified by FTIR, indicating the existence of mixed network Si–O–Zr in the coatings obtained by the different routes. Crystallisation of ZrO₂(t) was only observed at high sintering temperature (900^∘C) by FTIR and confirmed by DRX.     

Effects of aging time on V2O5 sol-gel coatings

Vanadium pentoxide (V₂O₅) sols have been used in conductive coatings and related applications [1, 2, 3]; however, the changes which may occur in the properties of these coatings with sols of different ages have not been carefully shown. Properties which may be dependent on the age of the sol (sol viscosity, film morphology and conductance) were measured in this work. The coating sols were prepared by ion-exchange of sodium metavanadate solutions.It was found that the coating thickness, sol viscosity, and surface morphology of the coatings were directly related to the age of the sol used. The dried coating thickness increased from 3 microns to 20 microns over a 30 day period. The sol viscosity increased from 1 centipoise to near 2 centipoise. The surface morphology of the coatings changed from that of a featureless surface at day 1 to a continual coverage of micron-sized fibers as the coating sols aged. The conductivity of the coatings, though, was unaffected by the age of the sol. The coating properties were correlated to the amount of polymerization of dissolved precursors in solution.     

Structure and associated properties of concentrated SiO2 sols in dilute salt solutions

Using the Verwey-Overbeek potential (VO) function the various liquid-state properties of SiO₂ sols in dilute salt solutions have been evaluated under the mean spherical model approximation (MSMA). The structure factors of these SiO₂ sols predicted by this model are compared with results obtained from small-angle neutron scattering experiments by Ramsay et al. Fourier transformation of these structure factors have been performed to obtain the radial distribution functions (RDF), and from these RDF's we computed coordination numbers of the sol particles. The interparticle distanced _c of sol particles has been obtained from the peak position in structure factorS(k) by using the Bragg's equation. The surface potential _s of the oxide sols has been determined from the amplitude (A) of the VO potential. The present calculations clearly indicate some sort of ordering in the sols system. It is gratifying to note that the present theoretical calculations could reproduce the available observed results very satisfactorily with respect to structure factor and other data.     

Electrochromism of NiO-TiO2 sol gel layers

Films of NiO-TiO₂ with Ni concentration of 100, 90, 87, 83, 75, 66, 50 and 33 mol% have been obtained via the sol-gel route by dip coating technique and sintered in air between 250 and 500°C using ethanolic sols of nickel acetate tetrahydrate (Ni(CH₃COO)₂·4H₂O) and titanium n-propoxide (Ti(O-CH(CH₃)₂)₄) precursors. Xerogels obtai- ned by drying the sols have been studied up to 900°C by thermal analysis (DTA/TG) coupled to mass and IR spectroscopy. The crystalline structure and morphology of the layers in the as deposited, bleached and colored states were determined by X-ray diffractometry, scanning electron microscopy and transmission electron microscopy Their electrochromic properties have been studied in 1 M KOH aqueous electrolyte as a function of the layer composition, thickness and sintering temperature. Deep brown colour with reversible transmittance changes have been obtained using cycling voltammetry and chronoamperometry processes. The best composition to get stable sols, a high reversible transmittance change and fast switching times (<10 s) was obtained with double NiO-TiO₂ layers 160 nm thick having 75% Ni molar concentration, and sintered between 300 and 350°C. The mechanism of coloration and morphology transformation of the layer during cycling are discussed in terms of an activation and degradation period. The results are in agreement with the accepted Bode model.     

Photophysical Properties of Coumarin‐30 Dye in Aprotic and Protic Solvents of Varying Polarities¶

Experimental results on various photophysical properties of coumarin‐30 (C30) dye, namely, Stokes' shift (Δv), fluorescence quantum yield (τ_f), fluorescence lifetime (τ_f), radiative rate constant (k_f) and nonradiative rate constant (k_nr), as obtained using absorption and fluorescence measurements have been reported. Though in most of the solvents the properties of C30 show more or less linear correlation with the solvent polarity function, Δf= [(ε ‐ 1)/(2ε+ 1) ‐ (n² ‐ 1)/ (2n²+ l)], they show unusual deviations in nonpolar solvents at one end and in high‐polarity protic solvents at the other end. From the solvent polarity and temperature effect on the photophysical properties of the dye, following inferences have been drawn: ( 1 ) in nonpolar solvents, the dye exists in a nonpolar structure, where its 7‐NEt₂ substituent adopts a pyramidal configuration and the amino lone pair is out of resonance with the benzopyrone π cloud; ( 2 ) in medium to higher polarity solvents, the dye exists in a polar intra‐molecular charge transfer structure, where the 7‐NEt₂ group and the 1,2‐benzopyrone moiety are in the same plane and the amino lone pair is in resonance with the benzopyrone π cloud; ( 3 ) in protic solvents, the dye‐solvent intermolecular hydrogen bonding influences the photophysical properties of the dye; and ( 4 ) in high‐polarity protic solvents, the excited C30 undergoes a new activation‐controlled nonradiative deexcitation process because of the involvement of a twisted intra‐molecular charge transfer (TICT) state. Contrary to most other TICT molecules, the activation barrier for this deexcitation process in C30 is observed to increase with solvent polarity. A rational for this unusual behavior has been given on the basis of the solvent polarity‐dependent stabilization and crossing of relevant electronic states and the relative propensity of interconversion among these states.     

Synthesis and Some Properties of Cerium Dioxide Hydrosols

Cerium dioxide hydrosols are synthesized by peptizing with nitric acid a precipitate obtained by hydrolyzing cerium(III) nitrate. The synthesized sols are stable with respect to aggregation in both acidic (pH 1.5–3.0) and alkaline media (pH 9.0–11.0). The mean hydrodynamic radius of particles is about 25 nm. The isoelectric point corresponds to pH 6.2. The phase composition of sol particles is determined by X-ray diffraction at pH of the dispersion medium ranging from 1.5 to 3.0. The sol coagulation thresholds are determined in the presence of sodium nitrate and sulfate, as well as of mixed magnesium salt at various pH values of the dispersion medium. Assumptions are made concerning the nature of the aggregative stability of sols.     

Microporous SiO2 and SiO2/MOx (M=Ti,Zr, Al) for ceramic membrane applications: A microstructural study of the sol-stage and the consolidated state

Microporous SiO₂ and SiO₂/MO₂ (M=Ti, Zr, Al; 10 mol% MO_x) materials for gas separation membrane applications have been prepared from polymeric sols. Characterization of these sols with SAXS showed that the mean fractal dimension of the SiO₂ sols is 1.3–1.4 with a radius of gyration of approximately 2.5 nm. The dried and calcined films are microporous and the pore size distribution was bimodal with maxima at diameters of 0.5 nm and 0.75 nm. For the SiO₂/TiO₂, SiO₂/ZrO₂ and SiO₂/Al₂O₃ systems, much milder reaction conditions proved to be necessary to obtain sols with comparable fractal dimensions due to the high reactivity of the Ti/Zr/Al-alkoxides. Microporous supported membranes with molecular sieve-like gas transport properties can be prepared from a relatively wide range of sol structures: from polymers too small to characterize with SAXS to structures with fractal dimensions: 1<d _f<2.04.     

Ultra-low expansion glass from gels

Pyrolysis of mixed titanium and silicon metal halides produces a commercial glass (7.4% TiO₂) with ultra-low thermal expansion that is essentially zero over the temperature range of 0 to 300°C. A colloidal particulate gel process involving potassium silicate, titania sol and formamide gel reagent was found to produce glass compositions with similar low expansion behavior. Due to the strongly basic nature of the precursor solutions, special titania sols had to be prepared that were stable in these alkali silicate solutions. The preferred TiO₂ sols were those containing quaternary ammonium stabilizing counter-ions. These sols served not only as the source of homogeneously distributed titania, but they may also serve as nucleating species that contribute to particle growth and pore size control of the gel network. The large pore (0.3 µm) TiO₂/SiO₂ gel structures were easily dealkalized, dried and sintered to uncracked glass shapes. Plates up to 9.5 cm×6.6 cm× 0.5 cm thick and some intricate cast shapes were produced and their glass properties evaluated.     

Chemistry of superacids

Superelectrophilic nitration of deactivated aromatics with NO₂Cl−3MX _n complexes in aprotic nonpolar solvents such as CH₂Cl₂ makes it possible to obtain the corresponding nitro derivatives in good to almost quantitative yields under mild conditions. For part 34, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 953–956, May, 1998.     

Studies on the Radical Cyclization of 3‐Oxopropanenitriles and Alkenes with Cerium(IV) Ammonium Nitrate in Ether Solvents

The radical cyclization of 3‐oxopropanenitriles 1a – 1e and alkenes 2a – 2g with cerium(IV) ammonium nitrate (CAN) in ether solvents was investigated (Tables 1 and 2). In the optimization study, 1,3‐dioxolane, 1,4‐dioxane, 1,2‐dimethoxyethane, Et₂O, and THF were used as ether‐based solvents, and the latter was found to be the most effective solvent in radical cyclizations mediated by cerium(IV). This system (cerium(IV)/THF) was applied to cyclizations of various 3‐oxopropanenitriles and 1,3‐dicarbonyl compounds with alkenes resulting in the formation of 4,5‐dihydrofurans in high yields (Table 2 and Scheme 2). The results of the cerium(IV)/THF radical cyclization were compared with those obtained with manganese(III) acetate/AcOH; the cerium(IV)/THF system turned out to be much more efficient.     

Optimization and stabilization of the antioxidant properties from Alkanet (Alkanna tinctoria) with natural deep eutectic solvents

Natural Deep eutectic solvents (NaDESs) are promising green solvents for the extraction of phytochemical compounds with antioxidant properties. In this study, we aimed to evaluate the behavior of the antioxidant properties of Alkanet (Alkanna tinctoria) root in hydrophilic NaDESs. For this purpose, two NaDESs constituted of sodium acetate:lactic acid (SALA₁₂) and sodium acetate:formic acid (SAFA₁₂) were synthesized to evaluate the antioxidant properties of Alkanet. 70% ethanol, 80% methanol and water were used as conventional solvents for comparison. SALA₁₂ and SAFA₁₂ were characterized considering their viscosities and FITR spectra. The extracts obtained with SALA₁₂ and SAFA₁₂ presented the best results when compared to the conventional solvents. The NaDES presented the highest extraction performance was SAFA₁₂. This prominent NaDES was subjected to the response surface methodology using a Box-Behnken design to figure out the optimum conditions to have the maximum antioxidant activity of Alkanet root. For total phenolic content (TPC), total flavonoid content (TFC) and DPPH radical scavenging, the optimum conditions were 1:4 molar ratio, 45% water content and 25% mL solvent ratio. The confirmed responses at the optimum conditions were 390.16 mg GAE/g, 10.69 mg ECE/g and 444.68 mmol TE/g, respectively. NaDES molar ratio and water content were found to impact most significantly the antioxidant properties Alkanet. The thermal stability experimentation revealed that phytochemicals along with the antioxidant properties of Alkanet were more stable in NaDES. These findings revealed that novel NaDES is an efficient green solvent for the extraction of bioactive compounds with antioxidant properties from plants.     

Investigations of MgF2 Optical Thin Films Prepared from Autoclaved Sol

MgF₂ thin films with ultra low refractive indices were obtained by sol–gel method using sols prepared from magnesium acetate and hydrofluoric acid. The sols were autoclaved in a Teflon cell at 100–180°C for 24 h and then coated on SiO₂ glass or CaF₂ crystal substrates by spin coating. Subsequently, the samples were heat treated at 150°C for 1 h. The optical properties of the thin films, such as refractive index and transmittance, were investigated in the UV region, especially in the deep UV (DUV, below 250 nm) region. Though the coatings consist of single layers, both samples exhibited high transmittance. In addition, they exhibit such antireflection effect over a very wide range of wavelength. Such a good antireflection effect was produced only by low refractive indices. It has also been confirmed that, even in the range of vacuum UV (VUV, 200–150 nm), CaF₂ samples with antireflection coatings could keep such a good antireflection effect.     

Properties of electrorheological fluids based on nanocrystalline cerium dioxide

Effect of conditions of nanocrystalline cerium dioxide preparation from aqueous solutions on its composition and physicochemical properties and on dielectric characteristics of CeO₂ suspensions in polydimethylsiloxane PMS-20 and the magnitude of electrorheological effect for these suspensions has been analyzed. Relationship between physicochemical properties of CeO₂ nanopowders and polarization and functional characteristics of electrorheological fluids derived therefrom has been established.     

Influence of CeO2 addition on the physicochemical and catalytic properties of Pd/TiO2 catalysts in CO oxidation

The influence of CeO₂ addition on the formation of the microstructure, electronic state, and catalytic properties of Pd/TiO₂ supported catalysts in CO oxidation were investigated. It was shown that, when Pd is supported on titanium dioxide modified with cerium dioxide, annealing at 500°C results in the formation of Pd/(CeO₂-TiO₂) catalysts with a nanocrystalline structure composed of incoherently intergrown fine anatase crystals and interblock boundaries in which palladium and cerium are stabilized. The higher catalytic activity of Pd/(CeO₂-TiO₂) catalysts compared to Pd/TiO₂ catalysts is explained by the smaller size of Pd particles and the higher proportion of palladium in the Pd^δ+ state.     

Density functional study on electronic and optical properties of C (or N)-doped cubic cerium dioxide

Density functional calculations were performed on electronic and optical properties of C (or N)-doped cubic cerium dioxide (CeO₂). When O is replaced by C (or N) in CeO₂, obvious band-gap (E_g) reduction is observed. Meanwhile, it is interesting to find that the substitutional doping of C (or N) in CeO₂ obviously increases the O 2p–Ce 4f transition intensity and also the refractive index. The increase in the O 2p–Ce 4f transition intensity on going from undoped, N-doped and C-doped CeO₂ was related to the covalent character of the Ce–O bond. Compared with the undoped CeO₂, the C (or N)-doped CeO₂, with steep absorption peaks at lower energy, can be used for visible-light absorption applications.     

Thermal decomposition of cerium(III) perchlorate

Thermal decomposition of Ce(ClO₄)₃ ? 9H₂O and Ce(ClO₄)₃ to give cerium(IV) dioxide in the temperature range 240–460°C was studied by DSC–TGA, X-ray powder diffraction, IR and mass spectroscopy. The thermolysis of these salts was shown to proceed through the stage of formation of intermediate product supposedly cerium oxoperchlorate. The thermal decomposition of cerium(III) perchlorate hydrate at 460°C leads to formation of nanocrystalline cerium dioxide with particle size of 13 nm.