pH值对Ni/CuO-ZrO2-CeO2-Al2O3催化剂甲烷自热重整制氢性能影响

采用浸渍-共沉淀法制备了Ni/CuO-ZrO2-CeO2-Al2O3催化剂,其中Ni负载量为10%(质量分数)。采用XRD、H2-TPR等方法表征了催化剂的结构及还原性能,并在固定床微反装置中考察了载体制备的沉淀过程中pH值的改变对Ni/CuO-ZrO2-CeO2-Al2O3催化剂在甲烷自热重整制氢反应中催化性能的影响。研究发现,在反应温度为650℃～850℃范围内,pH值为9制备的Ni/CuO-ZrO2-CeO2-Al2O3催化剂的甲烷转化率最高。由TPR与XRD结果可知,在制备条件中pH值为9的催化剂载体中ZrO2进入CeO2的晶格中,形成更多的CeO2-ZrO2固溶体,使得NiO与载体之间的相互作用增强,从而提高了甲烷的转化率。     

聚合物稳定的Au-Pd/TiO2-Al2O3催化剂的还原方法及其催化性能的研究

以PVP为稳定剂，乙醇和K1BH4为还原剂制备了Au-Pd／TiO2-Al2O3催化剂，考察了还原剂对Au-Pd负载型双金属催化剂加氢脱硫性能的影响，并运用XRD，TPD，TPR等技术对催化剂进行表征。结果表明，以乙醇还原的Au-Pd／TiO2-AlO3催化剂的加氢脱硫活性较好。乙醇还原的Au-Pd／TiO2．Al2O3催化剂中Au-Pd之间及活性组分与载体之间的相互作用较强，形成Au-Pd，合金的晶粒较小，活性组分的分散度和活性表面积较大，反应活化能较低，这些均有利于催化剂活性的提高。     

铈对Ru/γ-Al2O3变换催化剂的改性研究

采用浸渍法制备了一系列钌基催化剂,以水煤气变换为探针反应,采用XRD、TPR和TPD等手段研究了铈对Ru/γ-Al2O3催化剂的改性机制.结果表明,铈的加入显著地提高了Ru/γ-Al2O3催化剂的变换反应活性,增加了Ru/γ-Al2O3催化剂的活性中心数,降低了催化剂的还原温度,增强了催化剂对H2O的吸附和活化作用.     

CuO/La2O3-Al2O3催化剂中CuO物种的迁移和高温固相反应

采用XRD、激光Raman光谱和TPR技术研究了CuO／La2O3-Al2O3催化剂中CuO高温迁移及固相反应。结果表明，800℃焙烧的CuO（20％）／La203（x％）-Al2O3催化剂，低La2O3负载量（5％和10％）时，La2O3（x％）-Al2O3载体表面即存在CuO和少量CuAl2O4；当La2O3负载量增大（≥20％）时，由于La2O3的阻止作用，使得CuO无法迁移到La2O3内层和Al2O3反应生成CuAl2O4，从而使CuO稳定存在于催化剂表层。高温焙烧（≥900℃），La2O3的隔离作用下降，从而导致生成CuAl2O4。     

固体超强酸S_2O_8~(2-)/TiO_2-WO_3的制备及其催化性能研究

用溶胶-凝胶法制备了固体超强酸S2O82-/TiO2-WO3,并对其进行了XRD与IR表征,用乙酸乙酯合成模型反应考察了其催化性能,系统研究了WO3的含量、焙烧温度等制备条件对S2O82-/TiO2-WO3性能的影响。实验表明:在(NH4)10W12O41.xH2O质量分数为5.0%、焙烧温度为500℃条件下通过溶胶-凝胶法制备的固体超强酸S2O82-/TiO2-WO3,其载体为微细且晶格不太完整的锐钛矿型TiO2,比表面积较大,具有比浸渍法制备的SO42-/TiO2更高的硫含量和更强酸性,并具有较高的催化酯化活性和稳定性,在反应条件为:醇酸摩尔比1.48∶1、催化剂用量为冰醋酸的6.0%、反应时间2.0h,乙酸转化率可达74.1%(不加分水器)。催化剂在无需任何再生的条件下重复使用,活性下降趋势平缓,显示良好的稳定性。     

Cr--MnOx/TiO2--ZrO2低温选择催化还原NO的活性及抗毒性能

采用溶胶凝胶法制备TiO2-ZrO2载体,然后采用柠檬酸溶液浸渍法制备Cr-MnOx/TiO2-ZrO2复合催化剂.通过X射线衍射、比表面积测试(BET)、扫描电镜、X射线光电子能谱等测试方法对催化剂的物化性能进行表征分析,并进行NH3选择性催化还原NO实验,考察催化剂在低温下的活性及抗硫抗水性能.Cr元素介入到MnOx中,形成了新型的CrMn1.5O4活性物相,其中的Mn元素多以Mn3+和Mn4+存在.高价态的Cr5+使Mn元素由Mn3+向高氧化态的Mn4+转化,有利于低温选择性催化还原反应的进行.鉴于Cr元素第一电离能和电负性均低于Mn元素,能优先于Mn与SO2-4和SO2-3结合,保护MnOx不被硫酸化,从而提高Cr-MnOx/TiO2-ZrO2催化剂的抗毒性能.制备的五种不同Cr/(Cr+Mn)摩尔比的催化剂中,Cr(0.4)-MnOx/TiO2-ZrO2的性能最优,其颗粒分散均匀,具有较大比表面积,在180℃时脱硝效率能够达到95.8%,同时通入5%H2O和10-4SO2,脱硝效率缓慢下降,反应8h后,下降到73%,并保持稳定.     

ZrO2-Al2O3复合载体的制备方法对Pd基催化剂加氢脱硫性能的影响

采用连续流动微反装置考察了ZrO2-Al2O3复合载体制备方法对Pd基催化荆加氢脱硫性能的影响,并采用XRD,TPR,H2-TPD.NH3-TPD和H2吸附等技术对催化剂进行了表征.结果表明,复合载体的制备方法对Pd基催化剂加氢脱硫性能有较大的影响,与浸渍法相比,溶胶一凝胶法制备的复合载体增强了活性组分与载体的相互作用,有利于Pd分散度的增大和催化剂酸量的增加,从而有利于Pd基催化剂活性的提高.     

MnO_2/γ-Al_2O_3催化剂上3-戊酮的合成研究

采用γ-Al2O3为载体,金属氧化物为活性组分,以丙酸为原料,在固定床反应器上合成了3-戊酮。实验研究了γ-Al2O3上负载不同活性组分对反应收率的影响,确定了活性物质为MnO2时催化活性最高;研究了催化剂的负载量、浸渍时间、焙烧温度及实验反应温度对催化剂活性及反应产率的影响。结果表明,Mn的负载量为10%～13%,浸渍时间大于5 h,焙烧温度为450～600℃,焙烧时间为4～7 h制得的催化剂活性最优;较佳的反应温度范围为330～410℃。在此条件下,丙酸转化率大于95%,产物选择性大于90%。     

Zr对Pt-Sn/γ-Al2O3脱氢性能的影响

通过H2-TPR、H2化学吸附和O2-脉冲等物理化学表征手段,并结合丙烷脱氢催化性能测试,考察了助剂Zr对Pt-Sn/γ-Al2O3催化剂反应性能的影响,结果表明：少量Zr的添加可显著改善Pt-Sn/γ-Al2O3催化剂的脱氢稳定性,同时可提高丙烯选择性,降低催化剂表面积碳量.Zr的存在可能加强了Pt与助剂和载体之间的相互作用,提高Pt粒子抗烧结的能力.     

Zr对Pt-Sn/γ-Al_2O_3脱氢性能的影响

通过H2-TPR、H2化学吸附和O2-脉冲等物理化学表征手段,并结合丙烷脱氢催化性能测试,考察了助剂Zr对Pt-Sn/γ-Al2O3催化剂反应性能的影响,结果表明:少量Zr的添加可显著改善Pt-Sn/γ-Al2O3催化剂的脱氢稳定性,同时可提高丙烯选择性,降低催化剂表面积碳量.Zr的存在可能加强了Pt与助剂和载体之间的相互作用,提高Pt粒子抗烧结的能力.     

Superconducting Transition Temperature in YBa2Cu4O8/La2/3 Ca1/3 MnO3 / YBa2 Cu4O8 Heterostructure

YBa2Cu4O8/La2/3 Ca1/3 MnO3/YBa2Cu4O8 （ Y-124/LCMO/Y- 124） heterostructure was prepared by facing-target sputtering technique. The oscillatory superconducting transition temperature was observed when the thickness of LCMO d L is larger than critical thickness d L^CR. The metal-insulator transition temperature can only be detected at d L 〉 d L^CR. The dependence on the spacer layer in LCMO/Y-124 systems suggests strongly the interplay of ferromagnetic and superconducting couplings.     

CaO--TiO2--Fe2O3三元系中Ca3TiFe2O8的生成机理

钒钛磁铁矿是烧结矿重要的原料之一,Ca₃TiFe₂O₈作为钒钛烧结矿中矿物被发现之后,其生成机理尚不明确.本文采用X射线衍射分析、元素能谱分析和TG-DSC分析相结合的方法,研究了Ca₃TiFe₂O₈的生成机理以及不同温度、CaO与TiO₂含量下Ca₃TiFe₂O₈的生成规律.实验结果表明,Ca₃TiFe₂O₈由Ca₂ Fe₂O₅和CaTiO₃反应生成,即CaO和Fe₂O₃反应生成Ca₂ Fe₂O₅;其后,与CaTiO₃反应生成Ca₃TiFe₂O₈.反应时间越长,Ca₃TiFe₂O₈的生成量越大,但反应温度对Ca₃TiFe₂O₈生成的影响并不明显.另外,还发现CaO含量越高,Ca₃TiFe₂O₈越易于生成,而且等摩尔Fe₂O₃和CaO下只要存在TiO₂,就会有Ca₃TiFe₂O₈生成.      

Effect of Fe2O3 Loading Amount on Catalytic Properties of Monolithic Fe2O3/Ce0.67Zr0.33O2 -Al2O3 Catalyst for Methane Combustion

Ce0.67Zr0.33O2-Al2O3 solid solution was prepared by the co-precipitation method. Fe2O3-based catalysts supported on the solid solution were obtained by the impregnation method. The article revealed that the optimal loading amount of Fe2O3 on Ce0.67Zr0.33 O2-Al2O3 in our experimental condition for catalytic combustion of methane was 8% （ mass fraction）. The prepared catalysts were characterized by BET, TPR, XRD analyses, and their catalytic activity was investigated after being calcined at 873 K and after being aged in water gas at 1273 K. When the loading amount of Fe203 was 8% （ mass fraction）, the catalyst held the highest activity, and the best temperature speciality and thermal stability. The complete-conversion temperature of methane for fresh and aged sample was 788 and 838 K, respectively. The range between the light-off temperature and the complete-conversion temperature was only 15 K. The characterization results of XRD indicated that Fe2O3 was well dispersed on the Ce0.67Zr0.33O2-Al2O3 matrix. The results of BET and TPR were in good harmony with the catalytic activity results.     

Synthesis and Crystal Structure of A Bimetallic Terbium Complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3 （THF）3

The reaction of 2, 6-^iPr2CbH3NHSiMe3 with Tb（CH2SiMe3）3（THF）2 in benzene at room temperature afforded a binuclear terbium complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3（THF）3. X-ray diffraction revealed that Tb atoms were bridged by three methylene units. One Tb atom was six-coordinated by two nitrogen atoms, three methylene carbons, and one THF molecule, while the other Tb atom was six-coordinated by one nitrogen atom, three methylene carbons, and two THF molecules. Both Tb atoms adopted a distorted trigonal prism geometry.     

Study on thermal expansion behavior of Dy2O3 - Al2O3 - SiO2 glass

Employing Dy2O3, Al2O3, and SiO2 as starting materials, several series of Dy2O3-Al2O3-SiO2 sealing glass were prepared. The relationship between their coefficients of thermal expansion and the contents of Dy2O3, Al2O3, and SiO2 were studied respectively. Experimental results showed that Dy2O3 and Al2O3 had a positive effect on the coefficient of thermal expansion of glass, whereas, SiO2 had a negative effect. The coefficient of thermal expansion of glass showed an apparent linear relation to the contents of these three raw materials, from which an estimation model was built, to calculate the coefficient of thermal expansion of sealing glass. Relative errors of the calculating results to testing results were no more than 2%, which suggested that the estimation model was reasonable. This study provides a good theory reference for the practical utilizing of this sealing material, through which a proper glass composition for good sealing could be easily found.     

Solubility of carbon in CaO-B2O3 and BaO-B2O3 slags

The solubility of carbon in molten CaO-B₂O₃ and BaO-B₂O₃ slags at high temperatures was measured to understand the dissolution mechanism of carbon into the slags. The B₂O₃-bearing slags, which have a wide range of liquids, at the temperature of interest have been applied to investigate the effect of basicity on the solubility of carbon from the saturation of acidic or basic components. The solubility of carbon, as a function of the composition of slags, shows a minimum value, and it is suggested that carbon dissolves by different mechanisms in the acidic and basic slags, respectively. From the infrared spectra measurements, the wave number indicating the B-C bond was found to be about 1150 cm⁻¹ in the acidic region of slags; hence, the incorporation of carbon into the borate network was confirmed qualitatively. The carbide capacity was compared to the nitride capacity, showing that the dissolutions of carbon and nitrogen into the slags are similar.     

Catalytic Partial Oxidation of Methane over Ni/CeO2-ZrO2-Al2O3

Nickel catalysts supported on CeO2-ZrO2-CeO2,ZrO2-Al2O3 and Al2O3 were prepared and characterized by means of X-ray diffraction（XRD）,BET areas,H2 temperature-programmed reduction（H2-TPR）,and X-ray photoelectron spectroscopy（XPS）.Through the test of catalytic partial oxidation of methane（CPOM）,Ni/CeO2-ZrO2-Al2O3 displayed the highest activity,which resulted from its largest BET area and best NiO dispersion.Furthermore,Ni/CeO2-ZrO2-Al2O3 maintained a long-time stability in CPOM,which was attributed to its best coking resistance among all the prepared catalysts.     

Research on Y2O3：Eu Phosphor Coated with In2O3

Y2O3：Eu red phosphor for FED application was prepared by high temperature solid-state reaction. The In2O3 coating by precipitation method to the phosphor was applied and the analyses of XRD, Zeta potential, SEM, EDS and low voltage cathodoluminescence （CL） were conducted for investigating the coating effect. The results showed that In2O3 coating promoted the low voltage CL of the phosphor efficiently. The promotion was possibly due to the enhancement of the surface conductivity of the phosphor grains.     

CaO含量对CaF2-Al2O3-CaO-Ce2O3渣系中Ce2O3行为的影响

在Fe-Cr-Al合金中添加微量的稀土元素可显著改善合金的使用性能, 文中以电渣重熔生产Fe-Cr-Al合金所用稀土渣为研究对象, 根据离子-分子共存理论(IMCT)建立了1 823 K时CaF₂-Al₂O₃-CaO-Ce₂O₃四元渣系热力学质量作用浓度模型.结果表明:当渣系中CaO和Al₂O₃的质量百分数之比维持在1:1, 即w_CaO /w_Al2O3=1时, 随着Ce₂O₃含量增加, 渣中铈铝酸盐Ce₂O₃·Al₂O₃质量作用浓度(活度)显著增加, 但炉渣物相种类没有变化.渣系中Ce₂O₃含量分别在10 %, 20 %, 30 %, 40 %时, w_CaO /w_Al2O3值对组元活度的影响各不相同但有共同特征, 表现在处于约1.0~1.8时, CaO活度增加最迅速, Ce₂O₃活度增加, Ce₂O₃·Al₂O₃活度下降, 说明渣中CaO含量增加促进了Ce₂O₃·Al₂O₃分解而导致Ce₂O₃活度增加, 选取渣系进行熔融和X射线衍射实验, 用jade 5.0软件分析物相, 实验结果与计算一致.      

Visible luminescence of lanthanide ions in Ca3Sc2Si3O12 and Ca3Y2Si3O12

The crystalline materials Ca₃Sc₂Si₃O₁₂ and Ca₃Y₂Si₃O₁₂ were characterized by different crystal structures, as the former is a cubic garnet, while the latter is an orthorhombic compound. We investigated the optical spectroscopy of these materials doped with several trivalent lanthanide ions and compared the results for the two hosts. Polycrystalline samples were prepared by solid state reaction, both undoped and doped with the trivalent lanthanide ions Eu³⁺, Tb³⁺ and Sm³⁺. Emission, excitation and Raman spectra of these materials were measured at temperatures ranging from 300 to 10 K. The optical spectra were assigned and discussed, and the effects of the crystal structure of the host on the spectroscopic behaviour were addressed. The technological potential of these compounds in the field of optical materials and devices was discussed.