Influence of TiO2 and CeO2 on the hydrogenation activity of bulk Ni2P

TiO₂- and CeO₂-promoted bulk Ni₂P catalysts were prepared by impregnation and in-situ H₂ temperature-programmed reduction method. The prepared catalysts were characterized by XRD and XPS. The hydrogenation activities of the catalysts were studied using 1.5 wt.% 1-heptene in toluene and 1.0 wt.% phenylacetylene in ethanol as the model feeds. The results indicate that bulk Ni₂P possesses low hydrogenation activity but is tunable by simply controlling the content of the additives (TiO₂ or CeO₂), suggesting that TiO₂ and CeO₂ are effective promoters to enhance the hydrogenation activity of Ni₂P.     

Improvement of Pt/ZrO2 by CeO2 for high pressure CH4/CO2 reforming

CH₄/CO₂ reforming over Pt/ZrO₂, Pt/CeO₂ and Pt/ZrO₂ with CeO₂ was investigated at 2 MPa. Pt/ZrO₂, which shows stable activity under 0.1 MPa, and Pt/CeO₂ showed gradual deactivation with time at the high pressure. The deactivation was suppressed drastically on Pt/ZrO₂ with CeO₂ prepared by different impregnation order (co-impregnation of Pt and CeO₂ on ZrO₂, and consecutive impregnation of Pt and CeO₂ on ZrO₂). The amount of coke deposition was found insignificant and similar among all the catalysts (including Pt/ZrO₂ and Pt/CeO₂). Catalytic activity after the reaction for 24 h was in agreement with Pt particle size after the reaction for same period, indicating that the difference of the catalytic stability is mainly dependent on the extent of Pt aggregation through catalyst preparation, H₂ reduction, and the CH₄/CO₂ reforming. Pt aggregation and the amount of coke deposition were least pronounced on (Pt–Ce)/ZrO₂ prepared by impregnation of CeO₂ on Pt/ZrO₂ and the catalyst showed highest stability.     

SELECTIVE CARBON MONOXIDE OXIDATION IN H2-RICH GAS STREAM OVER Co3O4/CeO2/ZrO2, Ag/CeO2/ZrO2, AND MnO2/CeO2/ZrO2 CATALYSTS

Activity and selectivity of selective CO oxidation in an H₂-rich gas stream over Co₃O₄/CeO₂/ZrO₂, Ag/CeO₂/ZrO₂, and MnO₂/CeO₂/ZrO₂ catalysts were studied. Effects of the metaloxide types and metaloxide molar ratios were investigated. XRD, SEM, and N₂ physisorption techniques were used to characterize the catalysts. All catalysts showed mesoporous structure. The best activity was obtained from 80/10/10 Co₃O₄/CeO₂/ZrO₂ catalyst, which resulted in 90% CO conversion at 200°C and selectivity greater than 80% at 125°C. Activity of the Co₃O₄/CeO₂/ZrO₂ catalyst increased with increase in Co₃O₄ molar ratio.     

Crystal structure,microstructure, thermal expansion and electrical conductivity of CeO2–ZrO2 solid solution

CeO₂–ZrO₂ solid solution was synthesised by mechanical activation solid-state chemical reaction method and characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal dilatometer, Hebb–Wagner method and DC van der Pauw method. The effects of CeO₂ content on the crystal structure, microstructure, thermal expansion coefficient (TEC), electronic conductivity and total conductivity were investigated. XRD analysis showed that (25 and 75?mol-%) CeO₂–ZrO₂ solid solutions corresponded to tetragonal and cubic phase, and 50?mol-% CeO₂–ZrO₂ belonged to the mixture of tetragonal and cubic phases. SEM analysis showed that doping CeO₂ was helpful to the sinterability of CeO₂–ZrO₂ samples. The TECs increased from 13.27?×?10^?6 to 14.72?×?10^?6?K^?1 with increasing CeO₂ content. The electronic and total conductivities of 75?mol-% CeO₂–ZrO₂ were largest, reaching 1.02?×?10^?4?S?cm^?1 and 1.02?×?10^?2?S?cm^?1 at 850°C, respectively.     

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.     

Morphology-Controllable Synthesis of CeO2 on a Pt Electrode

Nanoscale cerium dioxides with shape of nanoparticles, nanorods, and nanotubes were electrochemically synthesized. The morphology of CeO₂ was modulated by changing electrode potential and potential direction. CeO₂ nanorods and CeO₂ nanotubes were synthesized via the potentiostatic and cyclic voltammeteric methods, respectively. The morphology and structure of the obtained CeO₂ were characterized by field emission scanning electron microscope (FESEM) and X-ray diffraction (XRD). A possible formation mechanism has been suggested to illuminate the relationship between the preparation condition and the morphology of CeO₂.     

Synthesis and electrochemical properties of CeO2 nanoparticle modified TiO2 nanotube arrays

In this paper, a cerium dioxide (CeO₂) modified titanium dioxide (TiO₂) nanotube array film was fabricated by electrodeposition of CeO₂ nanoparticles onto an anodized TiO₂ nanotube array. The structural investigation by X-ray diffraction, scanning electron microscopy and transmission electron microscopy indicated that the CeO₂ nanoparticles grew uniformly on the walls of the TiO₂ nanotubes. The composite was composed of cubic-phase CeO₂ crystallites and anatase-phase TiO₂ after annealing at 450 °C. The cyclic voltammetry and chronoamperometric charge/discharge measurement results indicated that the CeO₂ modification obviously increased the charge storage capacity of the TiO₂ nanotubes. The charge transfer process at the surface, that is, the pseudocapacitance, was the dominate mechanism of the charge storage in CeO₂-modified TiO₂ nanotubes. The greater number of surface active sites resulting from uniform application of the CeO₂ nanoparticles to the well-aligned TiO₂ nanotubes contributed to the enhancement of the charge storage density.     

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 electrochemical characterization of nano-CeO2-coated nanostructure LiMn2O4 cathode materials for rechargeable lithium batteries

LiMn₂O₄ spinel cathode materials were coated with 0.5, 1.0, and 1.5 wt.% CeO₂ by a polymeric process, followed by calcination at 850 °C for 6 h in air. The surface-coated LiMn₂O₄ cathode materials were physically characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron microscopy (XPS). XRD patterns of CeO₂-coated LiMn₂O₄ revealed that the coating did not affect the crystal structure or the Fd3m space group of the cathode materials compared to uncoated LiMn₂O₄. The surface morphology and particle agglomeration were investigated using SEM, TEM image showed a compact coating layer on the surface of the core materials that had average thickness of about 20 nm. The XPS data illustrated that the CeO₂ completely coated the surface of the LiMn₂O₄ core cathode materials. The galvanostatic charge and discharge of the uncoated and CeO₂-coated LiMn₂O₄ cathode materials were measured in the potential range of 3.0-4.5 V (0.5 C rate) at 30 °C and 60 °C. Among them, the 1.0 wt.% of CeO₂-coated spinel LiMn₂O₄ cathode satisfies the structural stability, high reversible capacity and excellent electrochemical performances of rechargeable lithium batteries.     

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.     

Synergic enhancement effect of zirconium oxide,cerium oxide and iron or cobalt oxide on the formation of isobutene from CO and H2

Fe₂O₃ or CoO modified CeO₂-ZrO₂ catalysts lead to four times higher yield of hydrocarbons than ZrO₂ with C₄ hydrocarbons selectivity of more than 50% and isobutene selectivity of more than 80%. XRD and XPS measurements suggested that the interaction of Fe or Co oxide with CeO₂ causes the higher Ce³⁺ concentration with their higher oxidation state. Their combination with ZrO₂ synergistically causes the active and selective formation of isobutene.     

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.     

Influence of composition of MgAl2O4 supported NiCeO2ZrO2 catalysts on coke formation and catalyst stability for dry reforming of methane

Dry reforming of methane was studied over Ni catalysts supported on γAl₂O₃, CeO₂, ZrO₂ and MgAl₂O₄ (670 °C, 1.5 bar, 16–20 l CH₄ ml_catalyst⁻¹ h⁻¹). It is shown that MgAl₂O₄ supported Ni catalysts promoted with both CeO₂ and ZrO₂ are promising catalysts for dry reforming of methane with carbon dioxide. Within a certain composition range, the simultaneous promotion with CeO₂ and ZrO₂ has great influence on the amount of coke and the catalyst service time. XRD analyses indicate that formation of crystalline Ce_xZr_1−xO₂ mixed oxide phases occurs on double promotion. In particular, incorporation of low amounts of Zr in the CeO₂ fluorite structure provides stable dry reforming catalysis. As shown with TPR, promotion leads to a higher reduced state of Ni. SEM, XRD and TPR analyses demonstrate that highly dispersed, doubly promoted Ni catalysts with a strong metal-support interaction are essential for stable dry reforming and suppression of the formation of carbon filaments.     

Synthesis of CeO2-ZrO2 solid solution by glycothermal method and its oxygen release capacity

The glycothermal (GT) reaction of Ce acetate and Zr alkoxide directly yielded CeO₂-ZrO₂ solid solutions in a region of low Ce content ≤40 mol%. Of the CeO₂-ZrO₂ solid solutions obtained by the GT method and subsequent calcination at 500 or 800 °C, the sample with 20 mol% Ce content had the largest BET surface area. This sample exhibited the highest Ce-based oxygen release capacity in the whole Ce/Zr composition range. The oxygen release capacities of CeO₂-ZrO₂ solid solutions synthesized by the GT method were much larger than those of the samples prepared by a coprecipitation (CP) method. The Reitveld analysis and the repetitive reduction-oxidation experiment indicated that the CeO₂-ZrO₂ solid solution synthesized by the GT method has a homogeneous structure as compared with that prepared by the CP method.     

Surface of LiCo1/3Ni1/3Mn1/3O2 modified by CeO2-coating

A novel method to improve the cycling performance of LiCo_1/3Ni_1/3Mn_1/3O₂ in lithium-ion batteries by 1.0 wt.% CeO₂-coating is presented in this work. The crystalline structure and morphology of the synthesized powder have been characterized by XRD, SEM, TEM and their electrochemical performances were evaluated by CV, EIS and galvonostatic charge/discharge tests. It is found that CeO₂ forms a layer on the surface of LiCo_1/3Ni_1/3Mn_1/3O₂ without destroying the crystal structure of the core material. Electrochemical test indicates that CeO₂-coating could improve the cycling performance of LiCo_1/3Ni_1/3Mn_1/3O₂. At room temperature, the capacity retention of 1.0 wt.% CeO₂-coated material is 93.2% after 12 cycles at 3.0 C while that of the bare sample is only 86.6%. ICP-OES proves the coating layer could protect the dissolution of the transition metal ions from LiCo_1/3Ni_1/3Mn_1/3O₂. From the analysis of EIS, the improvement of cycle ability could be attributed to the suppression of the reaction between cathode and electrolyte.     

Oxygen storage capacity of promoted Rh/CeC2 catalysts. Exceptional behavior of RhCu/CeO2

The effect of various additives (V, Cr, Mn, Fe, Co, Ni, Cu and Pb) on the oxygen storage capacity (OSC) of CeO₂ and Rh/CeO₂ catalysts was investigated. Copper is an excellent promoter of OSC conferring to Rh a very high resistance to sintering (900°C, 2% O₂).     

Highly active and coking resistant Ni/CeO2-ZrO2 catalyst for partial oxidation of methane

Nickel catalysts over the CeO₂-ZrO₂ solid solution were successfully prepared by the co-precipitation method for partial oxidation of methane. The structures of the catalysts were systematically examined by N₂ adsorption/desorption, CO chemisorption, X-ray diffraction (XRD) and H₂-TPR techniques. The catalytic performance and carbon deposition were investigated for partial oxidation of methane as well. The results showed that the Ni/CeO₂-ZrO₂ catalysts had a large BET area and fine Ni dispersion. By the co-precipitation method, Ni and CeO₂-ZrO₂ solid solution had strong interaction confirmed by the H₂-TPR analysis. The Ni/CeO₂-ZrO₂ catalysts showed high activity and stability and the Ni/Ce_0.25Zr_0.75O₂ exhibited the best activity and coking resistance among these catalysts. The catalytic activities and coking resistant behaviors of catalysts were affected by the surface and structural properties of the catalysts.     

Characterization and Catalytic Properties of Combustion Synthesized Au/CeO2 Catalyst

Ceria-supported Au catalyst has been synthesized by the solution combustion method for the first time and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Au is dispersed as Au⁰ as well as Au³⁺ states on CeO₂ surface of 20-30 nm crystallites. On heating the as-prepared 1% Au/CeO₂ in air, the concentration of Au³⁺ ions on CeO₂ increases at the expense of Au⁰. Catalytic activities for CO and hydrocarbon oxidation and NO reduction over the as-prepared and the heat-treated 1% Au/CeO₂ have been carried out using a temperature-programmed reaction technique in a packed bed tubular reactor. The results are compared with nano-sized Au metal particles dispersed on -Al₂O₂ substrate prepared by the same method. All the reactions over heat-treated Au/CeO₂ occur at lower temperature in comparison with the as-prepared Au/CeO₂ and Au/Al₂O₂. The rate of NO + CO reaction over as-prepared and heat-treated 1% Au/CeO₂ are 28.3 and 54.0 mol g^-1 s^-1 at 250 and 300 °C respectively. Activation energy (E _a) values are 106 and 90 kJ mol^-1 for CO + O₂ reaction respectively over as-prepared and heat-treated 1% Au/CeO₂ respectively.     

Mesoporous CeO2 Catalyst Synthesized by Using Cellulose as Template for the Ozonation of Phenol

Mesoporous CeO₂ was synthesized by a sol-gel method using the biological renewable microcrystalline cellulose (MCC) as the template and Ce(NO₃)₃?6H₂O as the precursor of CeO₂. XRD, TEM, N₂ adsorption–desorption, and XPS were used for mesoporous CeO₂ characterization. The results show that CeO₂ nano-particles possess an average size of 7 ~ 10 nm, and specific area of CeO₂ synthesized with MCC template is approximately 5.5 times higher than CeO₂ synthesized without MCC. The ozonation catalyzed by CeO₂-T (with MCC) could remove 91.7% of phenol compared to 51.6% for single ozonation and 68.3% for CeO₂-W (without MCC) catalyzed ozonation. The COD removal efficiency is significantly higher for ozonation with CeO₂-T (69.2%) than that of CeO₂-W (49.5%) or ozonation alone (21.0%). The good performance of CeO₂-T is attributed to the high specific area and Ce(III)/Ce(IV) redox couple. During catalytic ozonation, the activation energy of catalytic ozonation (20.7 kJ mol^?1) is much lower than that of single ozonation (54.7 kJ mol^?1).     

Evaluation of oxygen storage profile on CeO2–ZrO2 mixed oxides by periodic injections of O2 pulse and their reduction behavior

Oxygen storage profile on CeO₂–ZrO₂ mixed oxide (CZ) has been observed by periodic injections of O₂ pulse. The reduction behavior of oxygen after the O₂ pulse injection was also investigated using Temperature Programmed Reduction (TPR) method. The oxygen storage profiles of the CZ catalyst with κ-CeZrO₄ phase indicate that the solid solution phase facilitates to diffuse oxygen into the bulk, and TPR profiles suggest that oxygen is preferentially stored by the reaction with Ce³⁺ species derived from CeO₂ phase compared with those from the κ-CeZrO₄ phase, especially at low temperatures.