Role of SiO2 in synthesis of SiO2-supported CeO2 composites

Pure and SiO₂-supported CeO₂ samples were prepared by Ce(NO₃)₃ decomposition, precipitation, and sol–gel methods in an attempt to study the role of SiO₂ in the synthesis of these materials. During synthesis process, SiO₂ support uniformly adsorbed cerium ions in aqueous solution, preventing nucleation and crystal growth of CeO₂ during the subsequent water evaporation and calcination steps. Uniform adsorption and inhibition were enhanced by NH₄⁺ and, to a larger extent, C₅H₇O₅COO^-. Despite the dispersion of cerium ions on SiO₂ reduced the temperature at which CeO₂ was formed, crystal size and crystallinity of CeO₂ in composites were significantly lower than that of pure CeO₂ sample prepared by the same synthesis method and at the same temperature. Composites were quite stable upon increasing the temperature from 400 to 800?°C. Visible light absorption, reduction, and photocatalytic activity characteristics of CeO₂ were improved upon dispersion on SiO₂. This work can help synthetize supported oxides with high activity and thermal stability.     

Fine-sized LiNi0.8Co0.15Mn0.05O2 cathode particles prepared by spray pyrolysis from the polymeric precursor solutions

Fine-sized LiNi_0.8Co_0.15Mn_0.05O₂ cathode particles with high discharge capacities and good cycle properties were prepared by spray pyrolysis from the polymeric precursor solutions. The cathode particles obtained from the spray solution without polymeric precursors had irregular morphology and hardly aggregated morphology. On the other hand, the cathode particles obtained from the spray solution with citric acid and ethylene glycol had fine size and regular morphologies. The cathode particles obtained from the spray solution containing adequate amounts of citric acid and ethylene glycol had several hundreds nanometer and narrow size distribution. The maximum discharge capacity of the cathode particles was 218 mAh/g when the excess of lithium component added to the spray solution was 6 mol% of the stoichiometric amount to obtain the LiNi_0.8Co_0.15Mn_0.05O₂ particles. The discharge capacities of the fine-sized LiNi_0.8Co_0.15Mn_0.05O₂ particles dropped from 218 to 213 mAh/g by the 50th cycle at a current density of 0.1 C.     

Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.     

Evaluation of mechanically treated cerium (IV) oxides as corrosion inhibitors for galvanized steel

The use of cerium salts as corrosion inhibitors for hot dip galvanized steel has been object of a numerous studies in the last few years. The role of cerium ions as corrosion inhibitors was proved: cerium is able to block the cathodic sites of the metal, forming insoluble hydroxides and oxides on the zinc surface. This fact leads to a dramatic decrease of the cathodic current densities and, therefore, to a reduction the overall corrosion processes. On the other hand, the potential of cerium oxides as corrosion inhibitors was also proposed. However, the real effectiveness of this kind of anticorrosive pigments has not been clarified yet.In this work cerium (IV) oxides are considered as corrosion inhibitors for galvanized steel. The corrosion inhibition mechanism of mechanically treated (milled) CeO₂ alone and in combination with milled SiO₂ nanoparticles was investigated. For this purpose milled CeO₂, CeO₂ and SiO₂ milled together and milled SiO₂ particles were studied as corrosion inhibitors in water solution. Therefore, the different mechanically treated particles were dispersed in 0.1 M NaCl solution to test their effectiveness as corrosion inhibitors for galvanized steel. The galvanized steel was immersed in the different solutions and the corrosion inhibition efficiency of the different particles was measured by means of electrochemical techniques. For this purpose, electrochemical impedance spectroscopy (EIS) measurements were carried out, monitoring the evolution of the corrosion processes occurring at the metal surface with the immersion time in the solution. The effect of the different pigments was also investigated by carrying out anodic and cathodic polarization measurements. The polarization curves were acquired under conditions of varied pH. The experimental measurements suggest that the mechanical treatment performed on the SiO₂ and CeO₂ particles promote the formation of an effective corrosion pigment. The tests evidence also the beneficial effect of the CeO₂ milled particles when used in combination with the mechanically treated SiO₂ particles. It was proved that in alkaline conditions the effect of the mechanically treated CeO₂ and SiO₂ particles is dramatically increased.     

Direct synthesis of CeO2/SiO2 mesostructured composite materials via sol–gel process

A series of CeO₂/SiO₂ mesostructured composite materials was synthesized by sol–gel process using Pluronic P123 as template, tetraethylorthosilicate as silica source and hexahydrated cerium nitrate as precursor under acid condition. The as-synthesized materials with Ce/Si molar ratio ranging from 0.03 to 0.3 were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), laser Raman spectroscopy (LRS), and N₂ adsorption. Characterization revealed that all samples possess ordered hexagonal mesoporous structure similar to SBA-15 and possess high surface area, large pore volume and uniform pore size. The fact that cerium species are present as highly dispersed CeO₂ nanocrystals in hexagonal matrix was confirmed by XRD combined with high-resolution TEM and selected area electron diffraction (SAED) analysis. Introduction of ceria to silica matrix can cause a distortion of hexagonal ordering structure and decrease pore diameter and increase the wall thickness of mesopores. Moreover, it can be found that this sol–gel route is a feasible, effective and simple method for templating synthesis of CeO₂/SiO₂ composite materials.     

Oxidation of silicon nitride hot pressed with CeO2 and SiO2 additions

(CeO₂ + SiO₂)-doped hot pressed silicon nitride shows parabolic oxidation kinetics in dry flowing air at T = 773 to 1673 K. Possible oxidation mechanisms have been proposed. The apparent activation energy for oxidation ( 350 kJmol⁻¹) suggests migration of impurity cations through the grain boundary phase to the silicon nitride/oxide reaction interface as the probable rate-limiting step. The very low solubility of cerium in silicate melts appears to be an important factor for oxidation. Cristobalite and ceria were the main crystalline oxidation products, the genesis and morphology of CeO₂ crystals being strictly related to oxidation temperature and cooling rate. A previously unknown hexagonal high-temperature form of ceria crystallized in samples subjected to very fast quenching.     

Effect of molar ratio of TiO2/SiO2 on the properties of particles synthesized by flame spray pyrolysis

Titania (TiO₂)–silica (SiO₂) nanoparticles were synthesized from sprayed droplets of a mixture of TEOS and TTIP by flame spray pyrolysis (FSP). The effect of molar ratio between TEOS and TTIP in the mixture on the particle properties such as particle morphology, average particle diameter, specific surface area, crystal structure, etc., were determined using TEM, XRD, BET, and FT-IR. A UV-spectrometer was also used to measure the absorption spectrum and the band gap energy of the product particles. As the molar ratio of TEOS/TTIP increased by increasing TEOS concentration at the fixed TTIP concentration, the average particle diameter of the mixed oxide nanoparticles increased with maintaining uniform dispersion between TiO₂ and SiO₂, and crystal structure was transformed from anatase to amorphous. The band gap energy of the TiO₂–SiO₂ nanoparticles increased with respect to the increase of the molar ratio due to the decrease of width of UV-absorption spectrum. Photocatalytic activity of TiO₂–SiO₂ composite particles decreased with the concentration of TEOS.     

TiO2, TiO2/Ag and TiO2/Au photocatalysts prepared by spray pyrolysis

TiO₂, TiO₂/Ag and TiO₂/Au photocatalysts exhibiting a hollow spherical morphology were prepared by spray pyrolysis of aqueous solutions of titanium citrate complex and titanium oxalate precursors in one-step. Effects of precursor concentration and spray pyrolysis temperature were investigated. By subsequent heat treatment, photocatalysts with phase compositions from 10 to 100% rutile and crystallite sizes from 12 to 120 nm were obtained. A correlation between precursor concentration and size of the hollow spherical agglomerates obtained during spray pyrolysis was established. The anatase to rutile transformation was enhanced with metal incorporations and increased precursor concentration. The photocatalytic activity was evaluated by oxidation of methylene blue under UV-irradiation. As-prepared TiO₂ particles with large amounts of amorphous phase and organic residuals showed similar photocatalytic activity as the commercial Degussa P25. The metal incorporated samples showed comparable photocatalytic activity to the pure TiO₂ photocatalysts.     

Novel polyacrylonitrile nanocomposites containing Na-montmorillonite and nano SiO2 particle

Polyacrylonitrile (PAN)/Na-montmorillonite (Na-MMT)/SiO₂ nanocomposites were prepared via in situ emulsion polymerization. X-ray diffraction (XRD) results suggest that the Na-MMT layers are exfoliated during the polymerization process. As evidenced by the transmission electron microscope (TEM), the Na-MMT and nano SiO₂ particles exhibit good dispersion in the polymer matrix. It was found that the PAN/Na-MMT/SiO₂ nanocomposites exhibit considerably enhanced mechanical properties compared with the PAN/Na-MMT and PAN/SiO₂ nanocomposites.     

Autothermal reforming of ethanol for hydrogen production over an Rh/CeO2 catalyst

Hydrogen production from ethanol by autothermal reforming over an Rh/CeO₂ catalyst was investigated with a stoichiometric feed composition. Ethanol as well as the reaction intermediates like acetaldehyde and acetone was entirely converted to hydrogen and C1 products at 673 K, and methane steam reforming and reverse water gas shift were the major reactions above 823 K. The Rh/CeO₂ catalyst exhibited stable activity and selectivity during 70 h on-stream operation at 823–923 K without obvious deactivation evidenced by the constant effluent gas composition. Structural analysis of the used catalyst revealed that CeO₂ prevented effectively the highly dispersed Rh particles with sizes of 1–3 nm from sintering and thus maintained sufficient Rh–CeO₂ interfacial areas, which facilitated coke gasification through the high oxygen storage-release capacity.     

Enhanced electrochemical and thermal stability of surface-modified LiCoO2 cathode by CeO2 coating

CeO₂-coated LiCoO₂ particles were successfully synthesized by a sol-gel coating of CeO₂ on the surface of the LiCoO₂ powder and subsequent heat treatment at 700 °C for 5 h. The surface-modified and pristine LiCoO₂ powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Auger electron spectroscopy (AES), slow rate cyclic voltammogram (CV), and differential scanning calorimetry (DSC). Cyclic voltammetry curves suggested that the CeO₂ coating suppressed the phase transitions. Unlike pristine LiCoO₂, the CeO₂-coated LiCoO₂ cathode exhibited better capacity retention than the pristine LiCoO₂ electrode in the higher cutoff voltage. Differential scanning calorimetric data revealed the higher thermal stability of the CeO₂-coated LiCoO₂ electrode.     

A comparative study of the selective oxidation of NH3 to N2 over gold, silver and copper catalysts and the effect of addition of Li2O and CeOx

This paper describes the selective oxidation of ammonia into nitrogen over copper, silver and gold catalysts between room temperature and 400 °C using different NH₃/O₂ ratios. The effect of addition of CeO_x and Li₂O on the activity and selectivity is also discussed. The results show that copper and silver are very active and selective toward N₂. However the multicomponent catalysts: M/Li₂O/CeO_x/Al₂O₃ (M: Au, Ag, Cu) perform the best. On all three metal containing catalysts the activity and selectivity is influenced by the particle size and the interaction between metal particles and support.     

Protective properties of SiO2 with SiO2 and Al2O3 nanoparticles sol-gel coatings deposited on FeCrAl alloys

Five layer SiO₂ coatings containing SiO₂ or Al₂O₃ nanopowders were deposited on FeCrAl alloy support by sol-gel method. Studies of protective properties of the coatings were carried out during high temperature cyclic oxidation. Changes in surface topography, structure and chemical composition of the surface layer of FeCrAl alloy were investigated. It has been shown that the type of nanofillers present in the SiO₂ coating (about 2.5?wt%) affects morphology of Al₂O₃ growing scale and determines the heat resistance of FeCrAl alloy. The lowest relative mass change (approx. 1.3%) after 10 oxidation cycles in air at 900?°C (one cycle = 12?h) was measured for the samples with coatings containing hydrophilic nanosilica (Aerosil 380) as filler. The protective efficiency of the coatings in the process of high-temperature oxidation is from 66% to 85%. The thickness of the formed scale and the value of the parabolic rate constant depend on the type of nanopowder in the coating.     

Effect of preparation temperature on the formation of Sr2CeO4 phosphor particles in the spray pyrolysis

Sr₂CeO₄ phosphor particles were prepared by spray pyrolysis at various preparation temperatures. The effect of preparation temperatures on the morphology, crystal structure and photoluminescence characteristics of the post-treated Sr₂CeO₄ phosphor particles was studied. Phase pure Sr₂CeO₄ phosphor particles were not produced by spray pyrolysis without post-treatment. The optimum post-treatment temperature to produce the Sr₂CeO₄ phosphor particles with high photoluminescence intensity was 1,000 °C in spray pyrolysis. The spherical morphology of the as-prepared particles obtained at high preparation temperatures above 1,400 °C had maintained after post-treatment at 1,000 ‡C. The relative photoluminescence intensities of the Sr₂CeO₄ phosphor particles varied with the preparation temperatures in the spray pyrolysis. The as-prepared particles obtained by spray pyrolysis at preparation temperatures below 1,400 °C converted into phase pure Sr₂CeO₄ phosphor particles after post-treatment at 1,000 ‡C. The optimum preparation temperature of the as-prepared particles was 1,400 °C to produce the Sr₂CeO₄ phosphor particles with spherical shape and high photoluminescence intensity in the spray pyrolysis.     

Synthesis and characterization of highly stable optically passive CeO2-ZrO2 counter electrode

Transparent and adherent CeO₂-ZrO₂ thin films having film thicknesses ∼543-598 nm were spray deposited onto the conducting (fluorine doped tin oxide coated glass) substrates from a blend of equimolar concentrations of cerium nitrate hexahydrate and zirconium nitrate having different volumetric proportions (0-6 vol.% of Zr) in methanol. CeO₂-ZrO₂ films were polycrystalline with cubic fluorite crystal structure and the crystallinity was improved with increasing ZrO₂ content. Films were highly transparent (T ∼ 92%), showing decrease in band gap energy from 3.45 eV for pristine CeO₂ to 3.08-3.14 eV for CeO₂-ZrO₂ films. The different morphological features of the film obtained at various CeO₂-ZrO₂ compositions had pronounced effect on the ion storage capacity and electrochemical stability. CeO₂-ZrO₂ film prepared at 5 vol.% Zr concentration exhibited higher ion storage capacity of 24 mC cm⁻² and electrochemical stability of 10,000 cycles in 0.5 M LiClO₄ + PC electrolyte due to its film thickness (584 nm) coupled with relatively larger porosity (8%). The optically passive behavior of such CeO₂-ZrO₂ film (with 5 vol.% Zr) is affirmed by its negligible transmission modulation irrespective of repeated Li⁺ and electron insertion/extraction. The coloration efficiency of spray deposited WO₃ thin film is found to enhance from 47 to 107 cm² C⁻¹ when CeO₂-ZrO₂ is coupled as a counter electrode with WO₃ in an electrochromic device (ECD). These films can be used as stable ‘passive’ counter electrodes in electrochromic smart windows as they retain full transparency in both the oxidized and reduced states and ever-reported longevity.     

Synthesis and electrochemiluminescence of the CeO2/TiO2 composite

CeO₂/TiO₂ composite with kernel–shell structure was synthesized by a sol–gel process. The characterization results show that the composite is made up of anatase phase TiO₂ and cubic system CeO₂. The electrochemiluminescence (ECL) behavior of the CeO₂/TiO₂ composite was studied by a cyclic voltammetry in the presence of persulfate, and the effect factors on ECL emission were discussed. Based on a series of experiments, it is proposed that the strong dual ECL emission produced by the CeO₂/TiO₂ composite resulted from the benefit ECL effect of interface heterojunction in composite.     

Improvement of electrochemical stability of LiMn2O4 by CeO2 coating for lithium-ion batteries

CeO₂-coated LiMn₂O₄ spinel cathode was synthesized using two-step synthesis method. All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns. The results of the electrochemical performances on CeO₂-coated electrode are compared to those of electrodes based on LiMn₂O₄ spinel without CeO₂ coating. CeO₂-coated LiMn₂O₄ cathode improved the cycling stability of the electrode. The capacity retention of 2 wt% CeO₂-coated LiMn₂O₄ was more than 82% after 150 cycles between 3.0 and 4.4 V at room temperature and 82% after 40 cycles at elevated temperature of 60 °C. The amounts of dissolved manganese-ions in CeO₂-coated LiMn₂O₄ significantly are smaller than pristine LiMn₂O₄ systems especially at elevated temperatures. Surface-modified LiMn₂O₄ can suppress the dissolution reaction of manganese-ions at elevated temperature and clearly improve the cyclability of the spinel LiMn₂O₄ cathode materials.     

Synthesis, characterization and enhanced photocatalytic activity of TiO2/SiO2 nanocomposite in an aqueous solution and acrylic-based coatings

In this study, TiO₂/SiO₂ nanocomposites were synthesized via a sol-gel route by adding tetraethylorthosilicate (TEOS) to a solution containing different molar ratios of Degussa P25 TiO₂ nanoparticles. FTIR, TGA, EDAX and XRD techniques were used to characterize the modified nanoparticles. Photocatalytic activity of the nanoparticles in an aqueous solution and into the acrylic based coating was evaluated using colour coordinate data measurements, SEM analysis, gloss measurements and FTIR spectroscopy, in the presence of Rhodamine B (Rh.B) dyestuff, as a pollutant model, before and after exposure to the UVA (340 nm) irradiation and compared to their unmodified counterparts.The results showed that silica grafting effectively reduced the photocatalytic activity of the TiO₂ nanoparticles as evidenced by absorption spectra and colour changes of Rh.B aqueous solutions during the UVA irradiation. The results revealed the effectiveness of sol-gel route for preparation of TiO₂/SiO₂ nanocomposites. The optimum result was obtained with 1% molar ratio of TiO₂:TEOS. Addition of TiO₂/SiO₂ nanocomposites into the acrylic based coating revealed reduction of photo-degradation of Rh.B compared to untreated nanoparticles. Finally, inclusion of TEOS treated TiO₂ nanoparticles into the aqueous organic coatings, provides photocatalytic property and as a result, it can possibly be considered for self-cleaning coatings.     

Eu2O3/SiO2 nanocomposites obtained by extraction pyrolysis

The conditions of the formation of nanosized Eu₂O₃/SiO₂ composites were studied. Amorphous silicon dioxide was coated with europium oxide by extraction pyrolysis. The resulting samples were studied by X-ray phase analysis and atomic force microscopy. The Eu₂O₃/SiO₂ composites were tested as catalysts of CO conversion.