The Thermokinetics of the Formation Reactions of Cerium(III) n-dodecylbenzene Sulfonate and Cerium(III) Stearate

The thermokinetics of the formation reactions of cerium(III) n-dodecylbenzene sulfonate and cerium(III) stearate are studied by using a microcalorimeter. On the basis of experimental and calculated results, three thermodynamics parameters (the activation enthalpies, the activation entropies, the activation free energies), the rate constant, three kinetic parameters (the activation energies, the pre-exponential constant and the reaction order) and the enthalpies of the reaction of preparing cerium(III) n-dodecylbenzene sulfonate in the temperature range of 20–35°C and cerium(III) stearate in the temperature range of44.6–62.8°C are obtained. The results showed that the title reactions easily took place in the studied temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Oxygen exchange properties in the new pyrochlore solid solution Ce2Sn2O7-Ce2Sn2O8

The phase-pure cerium stannate pyrochlore (Ce₂Sn₂O₇) has been prepared for the first time. The structure and oxidation states of both cations were carefully reviewed, and the compound was unambiguously replaced within the rare-earth stannate series. As a consequence of the low stability of trivalent cerium in oxide phases, one oxygen per formula unit could be intercalated by calcination under O₂ at 400 °C, leading to the new Ce₂Sn₂O₈ pyrochlore. This latter phase is subject to oxygen under-stoichiometry from 400 to 700 °C. However, oxygen deintercalation seems to be in competition with cerium oxide segregation at high temperature, leading to the formation of cerium deficient pyrochlore phases.     

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.     

Spectroscopic Study of Cerium-Doped Silica Gel Monoliths and Their Densified Derivatives

Cerium is exploited as a probe cation for elucidating the structure of an alkoxide-derived silica gel and its progressive evolution to a glass network as a function of heat-treatment up to 1000°C. At intermediate temperatures, the host structure exhibits inhomogeneity due to insufficient formation of siloxane bonds, which is reflected by at least two different sites and co-ordination spheres (termed “high” and “low” water ligation) for cerium. This is proved by the response of the gels heated up to 700°C to rehydration. Further formation of Si−O−Si network (900°C) leads to the destruction of the “high water” sites of cerium and progression towards a glassy structure. It is, however, only after heat-treatment at 1000°C that a dense silica glass network, not responding to rehydration, is finally obtained with cerium ions embedded in it.     

Exploitation the unique acidity of novel cerium-tungstate catalysts in the preparation of indole derivatives under eco-friendly acid catalyzed Fischer indole reaction protocol

Solid acidic cerium tungstate catalysts containing different molar ratios of cerium and tungstate were prepared by direct solvothermal methodology. The structure of the prepared catalysts was deeply studied and confirmed based on different characterization techniques such as DTA-TGA, FTIR, Raman spectra, XRD and N₂ adsorption measurements. Moreover, FTIR and TPD of chemically adsorbed pyridine techniques were conducted to fully address the nature and the strength of the acidic sites of the prepared catalysts. The study showed that at a lower molar ratio of tungstate, the catalyst contains cerium oxide phase and slight participation of cerium tungstate phase, which gradually increases with further increase of tungstate molar ratio. This phase change was also accompanied by a noticeable change in the thermal stability, surface area and acidic properties of the prepared catalysts. Additionally, the techniques used to study the acidic properties showed an excellent enhancement in the acidic centers. It was also noted that the strength of these acidic centers reached the maximum in the case of using tungstate: cerium molar ratio 2:1 (CeW2.0) catalyst, and slightly decreased thereafter. By exploiting the acidic properties of the prepared catalysts, a series of indole derivatives were synthesized via the Fischer indole synthesis strategy. The results also showed that ～100% of indole derivatives were obtained using 0.02 g catalyst at 80 °C after 2 h only. Moreover, the Reuse experiment demonstrated the possibility of recycling and reusing the catalyst through many cycles with high efficiency, indicating its wonderful constancy and reusability.     

Preparation and Spectroscopic,Microscopic, Thermogravimetric,and Electrochemical Characterization of Silver-Doped Cerium(IV) Oxide Nanoparticles

Silver ion-doped cerium oxide nanoparticles were prepared by polyol-based coprecipitation. Here, the impact of silver doping is evaluated on the crystallographic, optoelectronic, thermogravimetric, and redox behavior of cerium oxide nanoparticles. Spectroscopic techniques were used to characterize the phase purity, crystallinity, morphological structure, and optical and redox properties of nanoproducts. X-ray diffraction confirmed the formation of well-crystallized cerium oxide tetragonal fluorite. The optical absorption spectra and band gap energy were significantly affected following doping that was influenced by the crystalline size. Temperature production reduction investigated the influence of silver concentration on the redox properties of cerium oxide nanoparticles. These catalysts were reversible in cyclic redox reaction to 500°C, nonpyrophoric, and therefore demonstrated potential for applications for hydrogen generation for fuel cells and electrochemical biosensors.     

Conditional solubility versus pO2− of cerium(III) oxide in molten equimolar NaCl+KCl at 727°C

Reactions between cerium trichloride and oxide ions were studied in NaCl+KCl (1/1) at 1000°K, by potentiometry with a calcia-stabilized zirconia membrane electrode. Titration curves clearly demonstrated the existence of soluble cerium oxychloride (CeO⁺) and precipitated cerium oxide (Ce₂O₃), with respective dissociation constants 10^?11 and 10^?30 (molality scale). The corresponding conditional solubility diagram {log S (Ce^III)=f(pO^2?)} is presented and discussed.     

Synthesis and Characterization of Indium-borate Glass-ceramics Containing Ho0.01Ce0.74Zr0.25O1.995 Nanorods via Incorporation Method

Glasses in the system 5In₂O₃·94Na₂B₄O₇ were fabricated via melt quenching technique. The amorphous nature of the quenched glasses was confirmed by X‐ray powder diffraction studies, and the infrared spectra of the glasses show no boroxol ring formation in the structure of these glasses. Differential thermal analysis is shown glass transition temperature 696°C and crystallization temperature 1151°C. A cerium‐zirconium mixed oxide Ce_0.75Zr_0.25O₂ and Ho‐doped cerium‐zirconium mixed oxide were obtained by solid‐state method. Then glass powder and Ho‐doped cerium‐zirconium mixed oxide were mixed. The mixture was heated in a crucible. The glass‐ceramic sample was obtained by pouring the melts on stainless steel. Obtained samples were annealed at 450°C for 1 h to remove thermal strain. Differential thermal analysis for glass‐ceramic sample is shown glass transition temperature 668°C and crystallization temperature 1159°C. The scanning electron microscopy study for glass‐ceramic indicates that the crystallized glass consists of rod‐like crystals with average diameter of about 38 nm dispersed in the glassy regions.     

Thermal Analysis,EPR and XPS Study of Vanadyl(IV) Oxalate Behavior on the Ceria Surface

The thermal decomposition of vanadyl oxalatesupported on CeO₂ solid in a flow of dried air was analysed by thermogravimetry (TG) and differential scanning calorimetry (DSC) from room temperature up to 350°C. TG and DSC results have demonstrated that after the impregnation of CeO₂ solid by a vanadyl oxalate solution, cerium and vanadium(V) oxalates were evidenced. This latter compound seems attached to cerium(III) of the partial reduced CeO₂ phase. This result was confirmed with the electron paramagnetic resonance(EPR) and X-ray photoelectron spectroscopy (XPS) techniques. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Formation of the structure of cerium oxide-modified titanium dioxide

The formation of the structure of titanium dioxide containing 3–15 wt % CeO₂ in a wide temperature range (300–850°C) has been investigated by X-ray powder diffraction, electron microscopy, and adsorption methods. Modification of titanium dioxide with cerium oxide causes the formation of nanostructured Ce-Ti-O compounds consisting of incoherently intergrown fine anatase crystallites. The crystallites are separated by interblock boundaries in which cerium ions are stabilized. The nanostructure formed in the Ce-TiO₂ oxide system stabilizes the anatase phase, prevents the sintering of anatase particles at high temperatures, and allows modified anatase to retain a larger specific surface area and a higher porosity upon heat treatment than pure titanium dioxide does.     

The thermal decomposition of the 5,7-dihalo-8-quinolinol rare earth metal chelates

The thermal decomposition of the 5,7-dichloro-, 5,7-dibromo- and 5,7-duodo-8-quinohnol chelates of lanthanum, cerium, praseodymium, neodymium, samarium and yttrium was investigated on the thermobalance. The chelates decomposed in the temperature range from 65 to 125°C while the oxide levels were obtained from 395 to 805°C Although the chelate thermal stability temperatures varied little with the chelating agent, the minimum oxide level temperatures were largely dependent on the halogen substitution on the 8-quinolinol molecule. Results of this study were correlated with previous studies on the rare earth metal chclatcs with 8-quinolinol and 2-methyl-8-quinolinol.     

Facile fabrication of cerium niobate nano-crystalline fibers by electrospinning technology

In this study, one-dimensional (1D) cerium niobate nano-crystalline fibers were first prepared by a facile sol–gel and electrospinning process, followed by heat treatment. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TG), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HR-TEM) were used to characterize the samples. It can be seen from SEM images that the as-prepared xerogel samples and those annealed at 900 °C presented uniform fibrous morphology, with the diameter of 100–300 nm and length of several centimeters. The XRD and FT-IR results showed that cerium niobate samples had well-crystallized phase of CeNbO_4.25 with the crystallite size of about 28.6 nm at a heat treatment temperature of 900 °C, which can also be validated with the TEM image. The AC impedance of annealed disks made from the CeNbO_4.25 nano-crystalline fibers has been probed.     

Properties of β-alumina doped with cerium

Cerium-doped β-alumina was prepared by sintering samples of β-alumina with Ce(III) nitrate or Ce(IV) oxide. The maximum solubility of cerium in β-alumina was determined to be ～ 10 w/o Ce using Vegard's Law. X-Ray absorption corrections were made for angles greater than 50°, using the wide-angle error function. The photoacoustic spectrum of cerium-doped β-alumina was determined and was consistent with the uv-visible absorption spectrum of Ce(IV) in an oxide lattice. Magnetic susceptibility measurements also indicated the existence of Ce(IV) in the β-alumina lattice. Conductivity values were measured on samples containing 2 and 4 w/o cerium. A decrease in conductivity compared to undoped β-alumina was similar to that found for Cr(IV)-doped β-alumina.     

Corrosion protection of aluminium alloy AA2024 with cerium doped methacrylate-silica coatings

The aim of this work is the synthesis and characterization of hybrid coatings doped with cerium salts for corrosion protection of AA2024. The control of the inorganic and organic polymerization process allows the preparation of coatings with an open structure and a hydrophilic character. These facts facilitate the incorporation and mobility of cerium ions through the structure, enhancing its ability to promote a self-healing mechanism. The thermal treatment of the coatings has been limited to 120 °C to preserve the mechanical properties of the alloy. The electrochemical behaviour of the coatings has been evaluated in 0.3 wt% NaCl solution by means of EIS technique. Electrochemical measurements evidence good barrier properties at initial immersion time, and signals of corrosion inhibition from cerium ions at long immersion times could be assigned to the increasing of the impedance modulus at low frequencies and the presence of cerium oxide/hydroxide precipitates.     

Effect of the cerium content on the activity of Cu-Ce-Al-O catalysts in the methanol steam reforming reaction in a flow reactor

The Cu_18.5Ce _x Al_{81.5 ? x} (where x = 2, 7.4, and 14) oxide catalysts were synthesized by coprecipitation and tested in the methanol steam reforming reaction in an integral flow reactor at 270°C. It was found that the activity of the catalysts increased with the calcination temperature and catalysts with intermediate cerium contents exhibited the highest activity; these catalysts exhibited the greatest values of S _BET and S _Cu. The phase analysis demonstrated that copper in these samples occurred almost entirely as a CuO-CeO₂ solid solution. The concentration of carbon monoxide at the reactor outlet decreased with the calcination temperature. For the most active sample with a cerium content of 7.4% calcinated at 700°C, the concentration of CO reached a minimum of no higher than 0.3%.     

Manganese(II) catalysed oxidation of glycerol by cerium(IV) in aqueous sulphuric acid medium: a kinetic and mechanistic study

The manganese(II) catalysed oxidation of glycerol by cerium(IV) in aqueous sulphuric acid has been studied spectrophotometrically at 25 °C and I = 1.60 mol dm⁻³. Stoichiometry analysis shows that one mole of glycerol reacts with two moles of cerium(IV) to give cerium(III) and glycolic aldehyde. The reaction is first order in both cerium(IV) and manganese(II), and the order with respect to glycerol concentration varies from first to zero order as the glycerol concentration increases. Increase in sulphuric acid concentration, added sulphate and bisulphate all decrease the rate. Added cerium(III) retards the rate of reaction, whereas glycolic aldehyde had no effect. The active species of oxidant and catalyst are Ce(SO₄)₂ and [Mn(H₂O)₄]²⁺. A mechanism is proposed, and the reaction constants and activation parameters have been determined.     

Electronic Metal-Support Interaction-Modified Structures and Catalytic Activity of CeOx Overlayers in CeOx/Ag Inverse Catalysts

Electronic metal-support interactions (EMSIs) of oxide-supported metal catalysts strongly modifies the electronic structures of the supported metal nanoparticles. The strong influence of EMSIs on the electronic structures of oxide overlayers on metal nanoparticles employing cerium oxides/Ag inverse catalysts is reported herein. Ce₂O₃ overlayers were observed to exclusively form on Ag nanocrystals at low cerium loadings and be resistant to oxidation treatments up to 250 °C, whereas CeO₂ overlayers gradually developed as the cerium loading increased. Ag cubes enclosed by {001} facets with a smaller work function exert a stronger EMSI effect on the CeO_x overlayers than Ag cubes enclosed by {111} facets. Only the CeO₂ overlayers with a fully developed bulk CeO₂ electronic structure significantly promote the catalytic activity of Ag nanocrystals in CO oxidation, whereas cerium oxide overlayers with other electronic structures do not. These results successfully extend the concept of EMSIs from oxide-supported metal catalysts to metal-supported oxide catalysts.     

A thermodynamic study of the complexation reaction for some amino acids with cerium(III) and yttrium(III)

The thermodynamic parameters for the complexation reaction of leucine, valine, proline and hydroxyproline with cerium(III) and yttrium(III) were determined potentiometrical1y in aqueous solution at 25, 35 °C and μ=0.1. The values for the formation constants have been reported. The values of enthalpy changes (ΔS) and entropy changes (ΔS) are positive for all systems. The chelation effect is believed to be essentially an entropy effect.     

Effects of Cerium Oxides on the Catalytic Performance of Pd/CNT for Methanol Oxidation

The carbon nanotubes supported palladium(Pd/CNT)nanocatalysts were modified by cerium oxides/ hydroxides and their catalytic performances for methanol oxidation were evaluated.Electrochemical measurements indicate that the introduction of cerium remarkably improves the catalytic activity of Pd/CNT catalysts towards methanol oxidation.X-Ray photoelectron spectra results reveal an interaction between palladium and cerium oxides.It is also observed that cerium-modified catalysts have excellent poison resistances,which is attributed to the poison-removal ability of cerium oxides/hydroxides.The highly oxidized cerium oxides/hydroxides have a strong ability to inhibit the accumulation of carbonaceous intermediates on the active sites of Pd catalysts.