The surface properties and the activities in catalytic wet air oxidation over CeO2-TiO2 catalysts

No-noble metal CeO₂-TiO₂ catalysts prepared by sol-gel method were developed and examined for catalytic wet air oxidation (CWAO) of acetic acid. The structure of the catalysts was measured by BET, SEM, XRD, XPS and DTA-TG. We investigated the effect of the interactions of Ce and Ti on the structure of CeO₂-TiO₂ catalysts. The mechanisms of the relationships between the different content of Ti and the activity of CeO₂-TiO₂ catalysts were discussed. The results showed that the average crystal size of CeO₂ decreased and the surface areas increased; the low valence of Ce³⁺ increase, and the chemisorbed oxygen slightly decreased with the increase of Ti content on the surface of CeO₂-TiO₂ catalysts. The order of the activity in CWAO of acetic acid followed: Ce/Ti 1/1 > Ce/Ti 3/1 > Ce/Ti 1/3 > Ce/Ti 5/1 > CeO₂ > TiO₂ > no catalyst. In CWAO of acetic acid, the optimal atomic ratio of Ce and Ti was 1, and the highest COD removal was over 64% at 230 °C, 5 MPa and 180 min reaction time over Ce/Ti 1/1 catalyst. The excellent activity and stability of CeO₂-TiO₂ catalysts was observed in our study.     

Effects of oxygen vacancies on the room-temperature ferromagnetism of Co-doped polycrystalline CeO2

Pure and Co-doped single-phase CeO₂ crystals were synthesized by a solid-state reaction method. Samples of different oxygen vacancy concentration were studied, including (1) as-sintered crystals, (2) powders ground from the same crystal, and (3) a cold-pressed pellet from the ground powder that was unannealed and annealed at 800 °C. By analyzing the magnetic behaviors, surface/volume ratio and O vacancy concentration, the effects of oxygen vacancies on the room-temperature ferromagnetism (RT-FM) of Co-doped CeO₂ were systematically investigated. The results confirm that the RT-FM observed in Co-doped CeO₂ has a direct relationship with the oxygen vacancy concentration, and support the oxygen vacancy mediated FM mechanism.     

Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides

We have investigated the geometric and electronic structures of the cerium oxide (CeO₂)-titanium dioxide (TiO₂) mixed oxides with various Ce/TiO₂ weight ratios prepared by the sol-gel method in detail by means of X-ray diffraction (XRD), high-resolution X-ray photoelectron spectroscopy (XPS), Raman spectroscopy excited by 325 and 514.5 nm lasers, and scanning electron microscope (SEM). Existence of cerium effectively inhibits the phase transition of TiO₂ from the anatase phase to the rutile phase. XRD peaks of TiO₂ anatase attenuate continuously with the increasing amount of CeO₂ in the mixed oxide, but the XRD peaks of cubic CeO₂ appear only after the weight ratio of Ce/TiO₂ reaches 0.50. The average crystalline sizes of TiO₂ anatase and cubic CeO₂ in CeO₂-TiO₂ mixed oxides are smaller than those in the corresponding individual TiO₂ anatase and cubic CeO₂. Raman spectroscopy excited by the 514.5 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.70 whereas Raman spectroscopy excited by the 325 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.90. XPS results demonstrate that Ti exists in the form of Ti⁴⁺ in the CeO₂-TiO₂ mixed oxide. Ce is completely in the form of Ce³⁺ in the mixed oxides with a 0.05 weight ratio of Ce/TiO₂. With the increasing weight ratio of Ce/TiO₂, Ce⁴⁺ dominates. On basis of these results, we proposed that CeO₂ initially nucleates at the defects (oxygen vacancies) within TiO₂ anatase, forming an interface bridged with oxygen between CeO₂ and TiO₂ anatase. At the interface, Ce species cannot substitute Ti⁴⁺ in the lattice of TiO₂ anatase whereas Ti⁴⁺ can substitute Ce⁴⁺ in the lattice of cubic CeO₂. The decreasing concentration of oxygen vacancies, the Ti-O-Ce interface, and the decreasing average crystalline size of TiO₂ anatase act to inhibit the phase transformation of TiO₂ anatase. With the increasing amounts of CeO₂, the CeO₂ clusters continuously grow and form cubic CeO₂ nanocrystals. Spectroscopic results strongly demonstrate that the surface region of CeO₂-TiO₂ mixed oxide is enriched with TiO₂.     

Influence of laser power on the orientation and microstructure of CeO2 films deposited on Hastelloy C276 tapes by laser chemical vapor deposition

CeO₂ films were prepared on LaMnO₃/MgO/Gd₂Zr₂O₇ multi-coated Hastelloy C276 tapes by laser chemical vapor deposition at different laser power (P_L) from 46 to 101 W. Epitaxial (1 0 0) CeO₂ films were prepared at P_L = 46-93 W (deposition temperature, T_dep = 705-792 K). Epitaxial CeO₂ films had rectangular-shaped grains at P_L = 46-77 W (T_dep = 705-754 K), while square-shaped grains were obtained at P_L = 85-93 W (T_dep = 769-792 K). CeO₂ films showed a columnar microstructure. Epitaxial (1 0 0) CeO₂ films with rectangular grains exhibited full width at half maximum of ω-scan on (2 0 0) reflection and ?-scan on (2 2 0) reflection of 3.4-3.2° and 6.0-7.2°, respectively. The deposition rate of the epitaxial (1 0 0) CeO₂ films had a maximum of 4.6 μm h⁻¹ at P_L = 77 W (T_dep = 754 K).     

Core/shell structured ZnO/SiO2 nanoparticles: Preparation, characterization and photocatalytic property

ZnO nanoparticles were prepared by a simple chemical synthesis route. Subsequently, SiO₂ layers were successfully coated onto the surface of ZnO nanoparticles to modify the photocatalytic activity in acidic or alkaline solutions. The obtained particles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS) and zeta potential. It was found that ultrafine core/shell structured ZnO/SiO₂ nanoparticles were successfully obtained. The photocatalytic performance of ZnO/SiO₂ core/shell structured nanoparticles in Rhodamine B aqueous solution at varied pH value were also investigated. Compared with uncoated ZnO nanoparticles, core/shell structured ZnO/SiO₂ nanoparticles with thinner SiO₂ shell possess improved stability and relatively better photocatalytic activity in acidic or alkaline solutions, which would broaden its potential application in pollutant treatment.     

Research on CeO2 cap layer for YBCO-coated conductor

Two groups of coated conductor samples with different thicknesses of CeO2 cap layers deposited by pulsed laser deposition （PLD） under the same conditions have been studied. Of them, one group is of CeO2 films, which are deposited on stainless steel （SS） tapes coated by IBAD-YSZ （IBAD-YSZ/SS）, and the other group is of CeO2/YSZ/Y2O3 multilayers, which are deposited on NiW substrates by PLD for the fabrication of YBCO-coated conductor through the RABiTS approach. YBCO film is then deposited on the tops of both types of buffer layers by PLD. The effects of the thickness of the CeO2 film on the texture of the CeO2 film and the critical current density （Jc） of the YBCO film are analysed. For the case of CeO2 film on IBAD-YSZ/SS, there appears a self-epitaxy effect with increasing thickness of the CeO2 film. For CeO2/YSZ/Y2O3/NiW, in which the buffer layers are deposited by PLD, there occurs no self-epitaxy effect, and the optimal thickness of CeO2 is about 50 nm. The surface morphologies of the two groups of samples are examined by SEM.     

Preparation, electronic structure, and photocatalytic properties of Bi2O2CO3 nanosheet

Bi₂O₂CO₃ nanosheet with a thickness of less than 20 nm was synthesized via hydrothermal and solvothermal process. The properties of the as-prepared nanosheet were characterized by X-ray diffraction, scanning electron microscopy, and diffuse reflectance spectra. The electronic structure was investigated using first-principle calculations. Application of the as-prepared Bi₂O₂CO₃ nanosheet in photocatalysis was also studied.     

蓝宝石衬底上Gd2O3掺杂CeO2氧离子导体电解质薄膜的生长及电学性能

采用反应磁控溅射方法,在(0001)蓝宝石单晶衬底上,制备了纳米多晶Gd₂O₃掺杂CeO₂(GDC)氧离子导体电解质薄膜,采用X射线衍射仪(XRD)、原子力显微镜(AFM)对薄膜物相、结构、粗糙度、表面形貌等生长特性进行了表征,利用交流阻抗谱仪测试了GDC薄膜不同温度下的电学性能;实验结果表明,GDC薄膜为面心立方结构,在所研究的衬底温度范围内,均呈强(111)织构生长;薄膜表面形貌随衬底温度发生阶段性变化：衬底温度由室温升高到300℃时, 关键词： 2O₃掺杂CeO₂电解质薄膜')" href="#">Gd₂O₃掺杂CeO₂电解质薄膜 反应磁控溅射 生长特性 电学性能     

Preparation of photocatalytic Fe2O3-TiO2 coatings in one step by metal organic chemical vapor deposition

There are two major difficulties in the TiO₂ liquid-solid photocatalytic system: effective immobilization of the TiO₂ particles; and improving the catalytic activity under visible light. To simultaneously solve these two problems, Fe₂O₃-TiO₂ coatings supported on activated carbon fiber (ACF), have been prepared in one step by a convenient and efficient method—metal organic chemical vapor deposition (MOCVD). XRD results revealed that Fe₂O₃-TiO₂ coatings mainly composed of anatase TiO₂, α-Fe₂O₃ phases and little Fe₂Ti₃O₉. The pore structure of ACF was preserved well after loading with Fe₂O₃-TiO₂ coatings. UV-vis diffuse reflectance spectra showed a slight shift to longer wavelengths and an enhancement of the absorption in the visible region for Fe₂O₃-TiO₂ coatings, compared to the pure TiO₂ sample. A moderate Fe₂O₃-TiO₂ loading (13.7 wt%) was beneficial to mineralizing wastewater because the intermediates could be adsorbed onto the surface of photocatalyst following decomposition. The stable performance revealed that the Fe₂O₃-TiO₂ coatings were strongly adhered to the ACF surface, and the as prepared catalysts could be reused showing potential application for wastewater treatment.     

Flowerlike PtCl4/Bi2WO6 composite photocatalyst with enhanced visible-light-induced photocatalytic activity

Flowerlike PtCl₄/Bi₂WO₆ composite photocatalyst was successfully synthesized through a simple two-step method involving a template-free hydrothermal process and the following impregnation treatment. The samples were fully characterized by the study of X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and UV-Vis absorption spectra. The results indicated that the doping of Pt species did not affect the crystal structure and the morphology of Bi₂WO₆ photocatalyst, but it had great influences on the photocatalytic activity of Bi₂WO₆ towards rhodamine-B (RhB) degradation. Besides, the Pt species was found to be present as PtCl₄ in the composite samples, and also an optimal Pt species content on the surface of Bi₂WO₆ photocatalyst was discovered with the highest photocatalytic ability. The improved photocatalytic performance could be ascribed to the enhanced interfacial charge transfer and the inhibited recombination of electron-hole pairs. Meanwhile, a possible mechanism for RhB photocatalytic degradation over PtCl₄/Bi₂WO₆ catalyst was also proposed.     

Effects of surface-modification with Bi2O3 on the thermal stability and photoinduced charge property of nanocrystalline anatase TiO2 and its enhanced photocatalytic activity

Bi₂O₃ surface-modified TiO₂ nanoparticle has been synthesized by sol-hydrothermal processes, followed by post-treatment with an appropriate amount of bismuth nitrate solution, and also characterized by XRD, Raman, BET, TEM, FT-IR, XPS, UV-vis DRS and SPS techniques. The effects of the surface-modification with Bi₂O₃ on the thermal stability, photoinduced charge separation and photocatalytic activity for degrading rhodamine B (or phenol) under ultraviolet (or visible) irradiation are investigated in detail, along with their relationships and the activity enhancement mechanisms are also suggested. The results show that the modification with Bi₂O₃ can improve the thermal stability of the as-prepared anatase crystallites, consequently enhancing the anatase crystallinity so as to promote the photoinduced charge separation. And the modification with Bi₂O₃ also extends the optical response range. It can be concluded that the activity enhancement of surface-modified TiO₂ is mainly attributed to the increase in the photoinduced charge separation rate and to the extent of the optical response range, compared with un-modified ones. Moreover, the inhibition phase transformation mechanism related to Bi₂O₃ is suggested.     

Synthesis and photoluminescent characteristics of Sr2CeO4 phosphors prepared via a microwave-assisted solvothermal process

Blue-light emitting Sr₂CeO₄ phosphors were successfully prepared via a microwave-assisted solvothermal method employing ethylene glycol as a solvent. The formation of Sr₂CeO₄ phase began when the solvothermally derived precursors were heated at 800 °C. With increase in heating temperatures, significantly enhanced excitation and emission intensities were observed because of an increase in the amount of Sr₂CeO₄. Heating at 1200 °C led to a substantial decrease in mission intensity due to thermal decomposition of Sr₂CeO₄ at elevated temperatures. The solvothermally derived Sr₂CeO₄ was found to exhibit higher emission intensity than the solid-state-reaction-derived phosphors. According to the deconvoluted emission spectra, two emission peaks are attributed to two metal-to-ligand charge-transfer states. Based on the deconvoluted results, a qualitative energy-level diagram of Sr₂CeO₄ was proposed. VUV-excited luminescence studies for Sr₂CeO₄ indicate that one peak at 193 nm is assigned to the charge-transfer transition between Sr²⁺ and O²⁻.     

XPS investigation of diffusion of two-layer ZrO2/SiO2 and SiO2/ZrO2 sol–gel films

Two-layer ZrO₂/SiO₂ and SiO₂/ZrO₂ films were deposited on K9 glass substrates by sol–gel dip coating method. X-ray photoelectron spectroscopy (XPS) technique was used to investigate the diffusion of ZrO₂/SiO₂ and SiO₂/ZrO₂ films. To explain the difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films, porous ratio and surface morphology of monolayer SiO₂ and ZrO₂ films were analyzed by using ellipsometry and atomic force microscopy (AFM). We found that for the ZrO₂/SiO₂ films there was a diffusion layer with a certain thickness and the atomic concentrations of Si and Zr changed rapidly; for the SiO₂/ZrO₂ films, the atomic concentrations of Si and Zr changed relatively slowly, and the ZrO₂ layer had diffused through the entire SiO₂ layer. The difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films was influenced by the microstructure of SiO₂ and ZrO₂.     

Selective CO oxidation in hydrogen-rich gas over CuO/CeO2 catalysts

A series of CuO/CeO₂ catalysts with different Cu-Ce compositions were synthesized by co-precipitation method and characterized by X-ray diffraction, H₂-TPR, CO-TPD, SEM and X-ray photoelectron spectroscopy (XPS) techniques. The effects of Cu-Ce composition and water vapor on the catalytic properties for the selective CO oxidation in the hydrogen-rich gas were investigated. The results indicated that CuO (10%)/CeO₂ catalyst remained the maximum CO conversion and selectivity at 140 and 160 °C, while the performance of CuO/CeO₂ catalysts deteriorated with the CuO molar ratio further increased. The interfacial CuO and CeO₂ interaction and synergistic effect enhanced the redox properties of CuO/CeO₂ catalyst and the highly dispersed copper species were proposed as the active sites for the selective CO oxidation. The blockage of catalytic active sites by absorbed water and the formation of CO-H₂O surface complexes reduced the activity of CuO (10%)/CeO₂ catalyst. The decreasing of surface lattice oxygen and absorbed oxygen species and the agglomeration of copper particles were the plausible interpretations for the deactivation of CuO (10%)/CeO₂ catalyst.     

Preparation and characterization of amine-functionalized SiO2/TiO2 films for formaldehyde degradation

This paper investigated the gaseous formaldehyde degradation by the amine-functionalized SiO₂/TiO₂ photocatalytic films for improving indoor air quality. The films were synthesized via the co-condensation reaction of methyltrimethoxysilane (MTMOS) and 3-aminopropyltrimethoxysilane (APTMS). The physicochemical properties of prepared photocatalysts were characterized with N₂ adsorption/desorption isotherms measurement, X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FT/IR). The effect of amine-functional groups and the ratio of MTMOS/APTMS precursors on the formaldehyde adsorption and photocatalytic degradation were investigated. The results showed that the formaldehyde adsorption and photocatalytic degradation of the APTMS-functionalized SiO₂/TiO₂ film was higher than that of SiO₂/TiO₂ film due to the surface adsorption on amine sites and the relatively high of the specific surface area of the APTMS-functionalized SiO₂/TiO₂ film (15 times higher than SiO₂/TiO₂). The enhancement of the formaldehyde degradation of the film can be attributed to the synergetic effect of adsorption and subsequent photocatalytic decomposition. The repeatability of photocatalytic film was also tested and the degradation efficiency was 91.0% of initial efficiency after seven cycles.     

Preparation and characterization of SiO2/ZrO2/Ag multicoated microspheres

A new type of multicoated silica/zirconia/silver (SiO₂/ZrO₂/Ag) core-shell composite microspheres is synthesized in this paper. In the process, ZrO₂-decorated silica (SiO₂/ZrO₂) core-shell composites were firstly fabricated by the modification of zirconia on silica microspheres through the hydrolysis of zirconium precursor. Subsequently, on SiO₂/ZrO₂ composite cores, silver nanoparticles were introduced via ultrasonic irradiation and acted as “Ag seeds” for the formation of integrate silver shell by further reduction of silver ions using formaldehyde as reducer. The resulting samples were characterized by transmission electron microscopy, X-ray diffraction, Fourier-transform infrared, energy-dispersive X-ray, and UV-vis spectroscopy, indicating that zirconia and silver layers were successfully coated on the surfaces of silica microspheres.     

Nanosized iron and chromium oxides supported on mesoporous CeO2 and SBA-15 silica: Physicochemical and catalytic study

Mesoporous ceria and SBA-15 silica were modified with iron and chromium oxide nanoparticles and characterized by XRD, N₂-physisorption, FTIR, UV-vis, Moessbauer spectroscopy and TPR-TG in hydrogen. Their catalytic behaviour in methanol decomposition to CO and hydrogen was also studied. Stabilization of mono- and bi-chromate species, FeO_x patches or isolated iron ions as well as Fe₂O₃ and Cr₂O₃ nanoparticles in different ratio depending on the nature of the porous matrix was observed. The simultaneous presence of iron and chromium oxides lead to change in their dispersion, providing easier reducibility, higher catalytic activity and stability of the obtained materials in comparison with the corresponding mono-component ones. The “intimate contact” at the interface of both loaded metal oxide nanoparticles and the support was discussed with respect to explain the differences in the state of the active ingredient and its specific catalytic behaviour.     

掺杂CeO2的75TeO2-25Nb2O5-5ZnO飞秒激光诱导瞬态光栅的研究

用泵浦探测技术研究了掺杂CeO₂的75TeO₂-25Nb₂O₅-5ZnO玻璃在飞秒激光诱导的瞬态光栅多级自衍射。从拉曼和吸收光谱中研究了玻璃的结构特性，并证明了此玻璃中存在Ce3+离子。这种瞬态光栅起因于光克尔效应，并通过Ce3+离子中1S0?1F3电子能级跃迁形成的激发态粒子数光栅而改善，一级衍射信号的转换效率可达到11%。这些实验结果显示了掺杂CeO₂的75TeO₂-25Nb₂O₅-5ZnO飞玻璃在全转换开关中具有广泛应用。     

Synthesis and characterization of TiO2/Fe2O3 core-shell nanocomposition film and their photoelectrochemical property

TiO₂/Fe₂O₃ core-shell nanocomposition film has been fabricated via two-step method. TiO₂ nanorod arrays are synthesized by a facile hydrothermal method, and followed by Fe₂O₃ nanoparticles deposited on TiO₂ nanorod arrays through an ordinary chemical bath deposition. The phase structures, morphologies, particle size, chemical compositions of the composites have been characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and ultraviolet-visible (UV-vis) spectrophotometer. The results confirm that Fe₂O₃ nanoparticles of mean size ca. 10 nm coated on the surface of TiO2 NRs. After depositing Fe₂O₃, UV-vis absorption property is induces the shift to the visible-light range, the annealing temperature of 600 °C is the best condition for UV-vis absorption property of TiO₂/Fe₂O₃ nanocomposite film, and increasing Fe content, optical activity are enhanced one by one. The photoelectrochemical (PEC) performances of the as-prepared composite nanorods are determined by measuring the photo-generated currents under illumination of UV-vis light. The TiO₂ NRs modified by Fe₂O₃ show the photocurrent value of 1.36 mA/cm² at 0 V vs Ag/AgCl, which is higher than those of unmodified TiO₂ NRs.     

CO2 laser assisted removal of UO2 and ThO2 particulates from metal surface

Pulsed laser assisted removal of uranium dioxide and thorium dioxide particulates from stainless steel surface have been studied using a TEA CO₂ laser. Decontamination efficiency is measured as a function of laser fluence and number of pulses. Threshold fluence for the removal of UO₂ particulates has been found to be lower than that required for the removal ThO₂ particulates. Usage of a ZnSe substrate, that is transparent to the laser wavelength used here, enabled us to decouple the cleaning effect arising out of absorption in the particulates from that in the substrate and has contributed towards understanding the mechanism responsible for cleaning. The experimental observations are also corroborated by simple theoretical calculations.