高比表面积纳米CeO_2的制备

采用模板法制备高比表面积纳米CeO_2. 详细考察了铈盐和NaOH滴加速度、晶化时间和温度、铈盐种类、表面活性剂用量等对CeO_2比表面、晶粒尺寸的影响. 结果表明, 当CeCl_3加入速度=2.5 ml·min~(-1)、 NaOH加入速度=3 ml·min-1、晶化温度=90 ℃、晶化时间=24 h、 CeCl3∶ C_(12)H_(25)SO_4Na∶ NaOH∶ H2O=1∶ 2.7∶ 7.3∶ 1100(摩尔比)、焙烧温度=200 ℃时, CeO_2的比表面积和晶粒尺寸分别为457 m~2·g~(-1)和2.0 nm. 这种高比表面纳米CeO_2与常规CeO_2相比, 具有独特的物理、化学性质, 有望成为一种应用广泛的新型材料.     

Surface and Texture Properties of Tb-Doped Ceria-Zirconia Solid Solution Prepared by Sol-Gel Method

The three-way catalysts （TWCs） promoters Ce0.6Zr0.4- x TbxO2-y were prepared by sol-gel method. BET surface areas analysis indicated that an increase of the dopant Tb content from x = 0.05 to x = 0.15 favors an increase of surface area from 66.8 to 80.4 m^2· g^-1 compared with the undoped sample Ce0 .6oZr0.40O2 65.1 m^2·g^- 1 after calcination at 650℃. Transmission electron microscopy （TEM） observation indicated that the doped samples have a higher thermal stability. The XRD and Raman spectra confirmed that the Ce0.6Zr0.4-xTbxO2-y cubic solid solution is formed. XPS analysis revealed that Ce and Tb mainly existed in the form of Ce^4＋ and Tb^3 ＋ , and Zr existed in the form of Zr^4＋ on the surface of the samples. The doped samples were homogenous in composition ; the introduction of Tb into the CeO2-ZrO2 promoters resuited in the formation of a solid solution, and the concentration of surface lattice oxygen was increased.     

Ti4+掺杂纳米CeO2的制备及其抗紫外性能

以Ce(SO4)2.4H2O为主要材料,采用超声-沉淀法制备了掺杂Ti4+的纳米CeO2,并研究了掺杂Ti4+离子对CeO2的晶型和抗紫外性能的影响。用X-ray衍射、傅立叶红外光谱仪、紫外分光光度计、对其进行了表征。测试结果表明,CeO2晶型为面心立方,粒径范围15nm～25 nm,并且CeO2的红外吸收峰明显发生蓝移。当Ti/Ce摩尔比为0.4∶1时吸收性能最好,使CeO2的光谱响应范围变宽。单体CeO2的紫外屏蔽范围在250nm～350 nm,掺杂了Ti4+离子的CeO2的紫外屏蔽范围在220nm～450 nm。     

Synthesis and Luminescent Properties of Superfine Sr2CeO4 Phosphors by Sol-Gel Auto- Combustion Method

Citric acid complexing sol-gel auto-combustion method was explored to synthesize superfine Sr2CeO4 phosphors using the inorganic salts Sr（NO3）2 and Ce（NO3）3 as raw materials together with citric acid （CA） as a chelating agent. TGDTA, XRD, SEM and photoluminescence spectra were used to investigate the formation process, microstructure and luminescent properties of the synthesized Sr2CeO4. The results show that the crystallization of Sr2CeO4 begins at about 800 ℃ and completes around 900 ℃ with an orthorhombic structure. When the calcination temperature is above 1000 ℃, Sr2CeO4 partly decomposes into SrCeO3. SEM studies show that the particles of Sr2CeO4 obtained at 900 ℃ are sphericallike shape and superfine with diameter below 100 nm. The excitation spectrum of the superfine Sr2CeO4 phosphors displays a broad band with two peaks around 290 and 350 nm respectively. The former peak is stronger than the latter one. This broad band is due to the charge transfer （CT） band of the Ce^4＋ ion. Excited by a radiation of 290 nm, the superfine phosphors emit a strong blue-white fluorescence, and the emission spectrum shows a broad band with a peak around 470 nm, which can be assigned to the f→t1g transition of Ce^4＋ . It is found that the emission intensity is affected by the calcination temperature.     

Synthesis and Characterization of Y-Doped Mesoporous CeO2 Using A Chemical Precipitation Method

Using cetyltrimethylammonium bromide （CTAB） as the template agent, cerium nitrate as the cerium resource, yttrium nitrate as the yttrium resource, and ammonium carbonate as the precipitating agent, mesoporous CeO2 powders doped with different yttrium contents were successfully synthesized using a chemical precipitation method, under an alkalescent condition. Properties of the obtained samples were characterized and analyzed with X-ray diffraction （XRD）, energy dispersive analysis of X-rays （EDAX）, transmission electron microscopy （TEM）, infrared （IR） absorbance, and the BET method. For the prepared samples with 20% （molar ratio） Y-doped content, a BET specific surface area of 106. 6 m^2 · g^- 1, with an average pore size of3~27 nm were obtained. XRD patterns showed that the doped samples were with a cubic fluorite structure. TEM micrographs revealed that the doped samples showed a spherical morphology with a diameter ranging from 20 to 30 nm and a round pore shape. IR results indicated that the Ce-O-Ce vibration intensity decreased as the Y-doped content increased. N2 adsorption-desorption isotherms showed that the samples possessed typical mesopore characteristics. The average pore size of the samples decreased alter mesoporous CeO2 was doped with yttrium, and the average pore size decreased largely as the Y-doped content increased.     

Effect of Preparation Method on Surface Area and Crystalline Form of CeO2-ZrO2 Solid Solution

TheCeO2 ZrO2 solidsolutionisacrucialcompo nentinthethree waycatalysts(TWCs)usedtocatalyzethesimultaneouspurificationofCO ,HCandNOxfromanautomobileexhaust [1～ 3] .Besidesafeasiblecatalyticactivity ,itshouldhavehighthermalstabilityandoxygenstoragecapacity(OSC) .InordertogainhighperformanceCeO2 ZrO2 solidsolution ,varioustechniqueshavebeendeveloped .ItwasshownthataneffectofpreparationmethodonthesurfaceareaandcrystallineformofCeO2 ZrO2 isveryobvious .Intheearliestwork ,theCeO2 ZrO…     

Preparation and Characterization of CeO2-ZrO2 Solid Solution Ultrafine Particles Using Reversed Microemulsion

The development of the TWCs (three-way cata-lysts) was dictated bythe need to si multaneously con-vert the three main pollutants inthe exhaust gases ,i .e .,hydrocarbons (HCs) ,COand NOxpresent in theautomotive exhaust to H2O, CO2and N2[1]. Highestconvers…     

Synthesis of Ti-Ce-Si Binary and Ternary Nanocomposite Photocatalyst by Supercritical Fluid Drying Technology

Recently,photodegratation of various organiccontaminants with powdered semiconductors as cata-lysts has received much attention for their potential inthe utilization of light energy.TiO2is one of the mostwidely used photocatalysts due toits relatively nontox-ic,high activity,strong oxidizing property,and excel-lent stability.However,some weaknesses such as poormechanic strength,compressive strength and thermalstability have li mited its industrial applications.Therefore,it is necessary to i mp…     

Preparation of Well Dispersed and Ultra-Fine Ce （Zr）O2 Mixed Oxide by Mechanochemical Processing

Ultra-fine CeO2-ZrO2 mixed oxide was successfully synthesized by wet-solid phase mechanochemical processing, Ce2(CO3)3·8H2O, ZrOCl2·xH2O and ammonia were used as reactants. It is found that the crystalline Ce2(CO3)3·8H2O and ZrOCl2·xH2O are changed to amorphous cerium and zirconium hydroxide precursor after milling with ammonia, and Ce0.15Zr0.85O2 mixed oxide with pure tetragonal phase structure and medium particle size(D50)less than 1μm is formed by calcining precursor over 673 K. The XRD patterns indicate that the crystal unite size increases with rising calcining temperature due to crystal growth. However, the particle size and BET surface area of the Ce(Zr)O2 mixed oxide decreases with rising calcining temperature, which may be attributed to the contract of particles and the vanish of holes inside grains.     

Preparation and Characterization of CeO2 Superfine Powder

The CeO2 superfine powder was prepared by the co-precipitation method, using the industrial grade Ce2(CO3)3 and NH4HCO3 as starting material and precipitating reagent, respectively. The precipitated precursons and the calcinated products were characterized by the thermogravimetric analysis/thermoanalysis (TGA/DTA), X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM). The results show that using NH4HCO3 as a precipitating reagent,the precipitate decomposed full as it was heated to 360℃. The CeO2 superfine powder formed by calcinating the precipitate belongs to a cubic CaF2-type structure and has the first mean particle diameter 140nm and second mean particle diameter 630nm. The CeO2 powder particles aggregate and grow with raising the calcination temperature.     

Catalytic combustion study of soot on Ce0.7Zr0.3O2 solid solution

The Ce0.7Zr0.3O2 solid solution and CeO2 were prepared using the sol-gel method. The phase structure, crystallite sizes and the reducibility of the catalysts were characterized by XRD and H2-TPR techniques. XRD results indicated that Zr^4＋ had replaced part of Ce^4＋ to form a fluorite-like solid solution, which was favorable to obtain ultrafine nanoparticles. The ratio of main HE consumption for Ce0.7Zr0.3O2：CeO2 was 4.4：1.0, implying that the solid solution could improve the reducibility compared to the single CeO2. The Ce0.7Zr0.3O2 solid solution catalyst showed a sharp combustion peak at 397 ℃, which was 200 ℃ lower than that of the single soot. The good catalytic activity of the Ce0.7Zr0.3O2 was attributed to the formation of nano-CeO2-based solid solution, which enhanced the reducibility and then improved the combustion activity. As Ce0.7Zr0.3O2 could be easily reduced to Ce0.7Zr0.3O2-x meanwhile, after oxygenation, the Ce0.7Zr0.3O2.x was recovered to Ce0.7Zr0.3O2 completely. A catalytic combustion reaction mechanism was proposed： the Ce0.7Zr0.3O2 was reduced to Ce0.7Zr0.3O2-x by the reaction with carbon and then it was recovered to Ce0.7Zr0.3O2-x by the interaction with O2.     

一步水热法合成3D花状CoS锂离子电池负极材料的组织及电化学性能研究

以CoCl2·6H2O和硫脲(CH4N2S)为原料,采用一步水热法,通过改变钴硫摩尔比和添加表面活性剂制备出两种不同形貌(3D花状和球状)的硫化钴(CoS)锂离子电池负极材料。结果表明,当钴硫摩尔比为1:1时,在180℃下水热反应12 h可得到3D花状CoS负极材料,其三维立体花状结构由纳米级层片组成;当钴硫摩尔配比为1:1,添加十六烷基三甲基溴化铵(CTAB),在180℃下反应12 h可制得由小颗粒聚结成的球状CoS负极材料。在0.1C电流密度下,3D花状CoS电池首次放电比容量为752m Ah·g^-1,并且具有良好的倍率性能;在1C电流密度下,经过200圈的循环测试后,3D花状CoS电池仍有较高的放电比容量(185 mAh·g^-1),远高于球状CoS电池(118.6 mAh·g^-1),并且没有衰减的趋势。     

共沉淀法制备稀土石榴石Ln3Al5O12(Ln=Y, Ce, Yb)

以Y2O3、Yb2O3、Al(NO3)3.9H2O和Ce(NO3)3.6H2O为原料,NH4HCO3、NH3.H2O做复合沉淀剂,用共沉淀法制备纳米稀土石榴石Ln3Al5O12(LnAG,Ln=Y,Ce,Yb)粉体。用TG/DTA、XRD、SEM、TEM等手段对LnAG前驱体及煅烧后的粉体进行表征。结果表明,用上述方法在1 000℃煅烧3h可得到分散性好、形状规则且粒径为50nm左右的Y3Al5O12、Yb3Al5O12、Y2.9Ce0.1Al5O12石榴石粉体,但不能得到Ce3Al5O12石榴石,合成石榴石粉体的最佳煅烧温度为1 050℃以上。     

不同沉淀剂制备氧化铈抛光粉

氧化铈(CeO₂)抛光粉在光学玻璃、手机盖板、集成电路等领域内有着广泛的应用。合成高端CeO₂抛光粉主要采用液相沉淀得到前驱体,再经过煅烧转型制得CeO₂。前驱体是决定CeO₂抛光粉性质和性能的关键因素之一。通过模拟工业上常用的制备方法,以氯化铈(CeCl₃)为铈源,使用碳酸钠(Na₂CO₃)、碳酸铵[(NH₄)₂CO₃]、碳酸氢铵(NH₄HCO₃)、二水合草酸(H₂C2O₄·2H₂O)和氢氧化钠(NaOH)为沉淀剂,合成了一系列CeO₂抛光粉的前驱体。利用X-射线衍射仪(XRD)、扫描电子显微镜(SEM)、激光粒度仪等手段表征了前驱体的晶相、形貌、粒度等性质,并研究了前驱体煅烧转型后的CeO₂性质及其对K9光学玻璃的...     

Effects of rare earth on microstructures and properties of Ni-W-P-CeO2-SiO2 nano-composite coatings

Ni-W-P-CeO2-SiO2 nano-composite coatings were prepared on common carbon steel surface by pulse electrodeposition of nickel, tungsten, phosphorus, rare earth (nano-CeO2) and silicon carbide (nano-SiO2) particles. The effects of nano-CeO2 concentrations in electrolyte on microstructures and properties of nano-composite coatings were studied. The samples were characterized with chemical compositions, elements distributions, microhardness and microstructures. The results indicated that when nano-CeO2 concentration was controlled at 10 g/L, the nano-composite coatings possessed higher microhardness and compact microstructures with clear outline of spherical matrix metal crystallites, fine crystallite sizes and uniform distribution of elements W, P, Ce and Si within the Ni-W-P matrix metal. Increasing the nano-CeO2 particles concentrations from 4 to 10 g/L led to refinement in grain structure and improvement of microstructures, while when increased to 14 g/L, the crystallite sizes began to increase again and there were a lot of small boss with nodulation shape appearing on the nano-composite coatings surface.     

Preparation of Fine Spherical Particle Sized Ceria by Precipitation Method with Ammonium Bicarbonate

Fine spherical panicle sized ceria (CeO2) was prepared by homogeneous precipitation method with ammonium bicarbonate as precipitant. The prepared CeO2 has the primary panicle size of 10-50nm when calcined between 400-700℃ analyzed by XRD and the aggregated particle size is about 300 nm measured by LASER panicle sizer. SEM, TGDTA and Zeta-potential analyzer were employed individually to study the morphology, and the fonnation of CeO2 product. It was found that excess NH4NO3 can serve as an sphericallization agent to prepare spherical Ce02 powder by precipitation method.     

Effect of yttrium addition on water-gas shift reaction over CuO/CeO2 catalysts

This paper presented a study on the role of yttrium addition to CuO/CeO2 catalyst for water-gas shift reaction. A single-step co-precipitation method was used for preparation of a series of yttrium doped CuO/CeO2 catalysts with yttrium content in the range of 0-5wt.%. Properties of the obtained samples were characterized and analyzed by X-ray diffraction (XRD), Raman spectroscopy, H2-TPR, cyclic voltammetry (CV) and the BET method. The results revealed that catalytic activity was increased with the yttrium content at first, but then decreased with the further increase of yttrium content. Herein, CuO/CeO2 catalyst doped with 2wt.% of yttrium showed the highest catalytic activity (CO conversion reaches 93.4% at 250℃) and thermal stability for WGS reaction. The catalytic activity was correlated with the surface area, the area of peak y of H2-TPR profile (I.e., the reduction of surface copper oxide (crystalline forms) interacted with surface oxygen vacancies on ceria), and the area of peak C2 and A1 (Cu0→Cu2+ in cyclic voltammetry process), respectively. Besides, Raman spectra provided evidences for a synergistic Cu-Ovacancy interaction, and it was indicated that doping yttrium may facilitate the formation of oxygen vacancies on ceria.     

Oxygen Storage Capacity of Pt-, Pd-, Rh/CeO2-Based Oxide Catalyst

CZO （CeO2-ZrO2） and CZYO （CeO2-ZrO2-Y2O3） series of mixed oxides were prepared by coprecipitaion, and a part of these oxides were loaded with precious metals （PM）. XRD, BET, and oxygen storage capacity （OSC） investigations were performed on samples aged at 750, 900, and 1050 ℃. It was observed that BET surface area and OSC showed a marked decrease in CeO2 aged at high temperature, and the erystallite size showed an obvious increase. The CZO samples consist of cubic- and tetragonal crvstal phases, and their crystallite size increase rapidly when aged at high temperature. The CZYO samples consist of single crystal phase when the content of Y exceeds 0.15 mol, and their erystallite size increases slowly during high-temperature aging. It is concluded that additive Y can stabilize the performance of CZYO oxides. In the aged CZO and CZYO mixed-oxide systems, addition of a small amount of precious metals （Pt, Pd, Rh） increased the rate of reduction and led to an obvious improvement in OSC. OSC of CZO and CZYO with precious metals are related to their composition and the type of precious metal.     

Influence of Nanometric Ceria Sol-gel Coating on Oxidation Behavior of Chromium at 1000℃

 Isothermal oxidation behavior of chromium with and without nanometric sol-gel CeO2 coating is studied at 1000℃ in air. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are used to examine the surface morphology and microstructure of their oxide films. It is found that ceria coating greatly improves the anti-oxidation property of chromium. Laser Raman spectrometer and X-ray diffraction spectrometer (XRD) are also used to study the stress level in oxide films formed on ceria-coated and ceria-free Cr. Secondary ion massive spectrum (SIMS) is used to examine Cr, O and Ce element distribution in depth in oxide films. Results show that nano-ceria application greatly reduces the growing speed and grain size of Cr2O3 film, and his fine grain-sized Cr2O3 film probably has better high temperature plasticity, i.e. oxide film relieves part of the compressive stress by means of creeping. Meanwhile, CeO2 changes the oxide film growing mechanism from predominant cation outward diffusion to anion inward diffusion. XRD and Raman testing results both show the stress declination effect due to nano-CeO2 application, and their discrepancy is analyzed concerning to the rare earth effect.     

烧结温度对锂离子电池负极材料Li4Ti5O12性能的影响

采用钛酸四丁酯为钛源、一水合氢氧化锂为锂源，利用水热法制备锂离子电池负极材料Li₄Ti₅O₁₂（LTO），研究了水热后不同烧结温度对LTO相组成、微观形貌及电化学性能的影响。结果表明:当煅烧温度分别为500、550、600、650、700℃时，烧结LTO均为尖晶石型；500、550、600℃烧结LTO的微观形貌为纳米片状结构，当温度升高到650℃时，LTO出现纳米棒状结构，随着温度继续升高，LTO在700℃时生成较厚的纳米片状结构；当烧结温度为650℃时，LTO的比表面积为94.5907 m2·g-1，气孔体积为0.9663 mL·g-1，此时Li₄Ti₅O₁₂的放电比容量达到最大值240 mAh·g-1；电流密度100 mA·g-1、循环260次条件下，LTO容量保持率达96.45%，电流密度为1和2 A·g-1、循环1000次条件下，LTO容量保持率达92.97%和77.21%。