X-ray diffraction study of the ultrathin Al2O3 layer on NiAl110

Ultrathin Al2O3 layers on alloys are used as templates for model catalysts, tunneling barriers in electronic devices, or corrosion-resistant layers. The complex atomic structure of well-ordered alumina overlayers on NiAl110 was solved by surface x-ray diffraction. The oxide layer is composed of a double layer of strongly distorted hexagonal oxygen ions that hosts aluminum ions on both octahedral and tetrahedral sites with equal probability. The alumina overlayer exhibits a domain structure that can be related to characteristic growth defects and is generated during the growth of a hexagonally ordered overlayer (Al2O3) on a body-centered cubic (110) substrate (NiAl).     

Alkali-stabilized Pt-OHx species catalyze low-temperature water-gas shift reactions

We report that alkali ions (sodium or potassium) added in small amounts activate platinum adsorbed on alumina or silica for the low-temperature water-gas shift (WGS) reaction (H(2)O + CO → H(2) + CO(2)) used for producing H(2). The alkali ion-associated surface OH groups are activated by CO at low temperatures (~100°C) in the presence of atomically dispersed platinum. Both experimental evidence and density functional theory calculations suggest that a partially oxidized Pt-alkali-O(x)(OH)(y) species is the active site for the low-temperature Pt-catalyzed WGS reaction. These findings are useful for the design of highly active and stable WGS catalysts that contain only trace amounts of a precious metal without the need for a reducible oxide support such as ceria.     

The silica-alumina system: stable and metastable equilibria at 1.0 atmosphere

Diffusion couples, consisting of sapphire and fused silica, which were annealed in the temperature range from 1678 degrees to 2003 degrees C and analyzed by electron beam microprobe, have provided data on the stable phase equilibrium of the silica-alumina system. Under stable equilibrium conditions, the intermediate compound of this system, mullite (3Al(2)O(3) . 2SiO(2)), melts incongruently at 1828 degrees +/- 10 degrees C and its solid solution field extends from 70.5 to 74.0 percent (by weight) alumina. The stable phase diagram is a composite of the two binary eutectic diagrams: silica-mullite in the absence of alumina and silica-alumina in the absence of mullite. Under metastable conditions, mullite melts congruently at approximately 1890 degrees +/- 10 degrees C and its solid solution field extends to approximately 83.2 percent (by weight) alumina.     

TiO2/MIL-53(Al)和TiO2/Al2O3催化剂的制备及其光催化性能研究

采用溶剂热法合成了MIL-53(Al),以此为载体负载TiO_2制备得到TiO_2/MIL-53(Al)光催化剂用于污水中次甲基蓝的催化降解研究,并与传统载体材料Al_2O_3负载的TiO_2催化剂的光催化效果进行比较。样品通过热重-差热扫描量热(TG-DSC)、红外光谱(FTIR)、扫描电镜(SEM)、X射线衍射(XRD)、N_2物理吸附-脱附等方法进行表征。采用光度吸收法分析污水中次甲基蓝的降解率,结果显示,TiO_2/MIL-53(Al)光催化剂对次甲基蓝的光催化降解率达到98.6%,而TiO_2/Al_2O_3光催化剂对次甲基蓝的降解率只有70.3%,TiO_2/MIL-53(Al)光催化剂对污水中次甲基蓝的降解去除能力明显优于TiO_2/Al_2O_3光催化剂对次甲基蓝的降解去除能力。     

KOH／Al2O3催化大豆油酯交换反应制备生物柴油

[目的]用固体碱催化剂催化酯交换反应制备生物柴油,以减少对环境造成的污染。[方法]以层析用中性氧化铝为载体,负载KOH并经高温焙烧处理制得KOH／Al2O3催化剂,催化大豆油酯交换反应制备生物柴油,系统地研究了催化剂的制备、酯交换反应等条件对大豆油转化率的影响。[结果]该催化剂对大豆油与甲醇酯交换反应有很高的催化活性。试验结果显示,当KOH负载量为10％,500℃焙烧3h,催化剂用量5％,醇油摩尔比12：1,酯交换反应仅2h,大豆油的转化率高达98．63％。[结论]KOH／Al2O3催化剂对大豆油与甲醇发生酯交换反应有很高的催化活性,且生产工艺简单,产品后处理方便,具有很大的应用价值。     

Mixed-phase oxide catalyst based on Mn-mullite (Sm, Gd)Mn2O5 for NO oxidation in diesel exhaust

Oxidation of nitric oxide (NO) for subsequent efficient reduction in selective catalytic reduction or lean NO(x) trap devices continues to be a challenge in diesel engines because of the low efficiency and high cost of the currently used platinum (Pt)-based catalysts. We show that mixed-phase oxide materials based on Mn-mullite (Sm, Gd)Mn(2)O(5) are an efficient substitute for the current commercial Pt-based catalysts. Under laboratory-simulated diesel exhaust conditions, this mixed-phase oxide material was superior to Pt in terms of cost, thermal durability, and catalytic activity for NO oxidation. This oxide material is active at temperatures as low as 120°C with conversion maxima of ~45% higher than that achieved with Pt. Density functional theory and diffuse reflectance infrared Fourier transform spectroscopy provide insights into the NO-to-NO(2) reaction mechanism on catalytically active Mn-Mn sites via the intermediate nitrate species.     

Structure of the hydrated alpha-Al(2)O(3) (0001) surface

The physical and chemical properties of the hydrated alpha-Al(2)O(3) (0001) surface are important for understanding the reactivity of natural and synthetic aluminum-containing oxides. The structure of this surface was determined in the presence of water vapor at 300 kelvin by crystal truncation rod diffraction at a third-generation synchrotron x-ray source. The fully hydrated surface is oxygen terminated, with a 53% contracted double Al layer directly below. The structure is an intermediate between alpha-Al(2)O(3) and gamma-Al(OH)(3), a fully hydroxylated form of alumina. A semiordered oxygen layer about 2.3 angstroms above the terminal oxygen layer is interpreted as adsorbed water. The clean alpha-Al(2)O(3) (0001) surface, in contrast, is Al terminated and significantly relaxed relative to the bulk structure. These differences explain the different reactivities of the clean and hydroxylated surfaces.     

H3PW12O40/Al2O3在制备农药中间体丙烯醛反应中的性能评价研究

[目的]研究H3PW12O40/Al2O3在制备农药中间体丙烯醛反应中的性能。[方法]采用等体积浸渍法制备了H3PW12O40/Al2O3催化剂,在常压连续流动固定床反应器中,对催化剂的活性稳定性进行了考察,同时利用BET、SEM和XRD等对反应前后的催化剂进行了基本表征。[结果]在反应过程中,催化剂上的积碳量呈上升趋势,尤其在催化剂活性增长期其积碳生成速率很快。较高的空速有利于减少催化剂上的积碳量。[结论]积碳可能是由丙烯醛在杂多酸催化剂上的聚合而产生的,它覆盖在催化剂表面,堵塞了孔道,从而引起了催化剂活性的降低。但积碳并没有破坏催化剂的结构,催化剂仍然保持Keggin结构,仍具有催化活性。     

柠檬酸对纳米氧化铁诱导水稻根表铁膜形成及对水稻铁吸收转运的影响

本研究利用水培模拟实验探讨了柠檬酸对纳米氧化铁(NPs,γFe_2O_3)诱导水稻根表铁膜的影响,同时研究了其对铁(Fe)在植株体内吸收转运的影响。结果表明,低浓度柠檬酸包被和未包被处理NPs能够显著增加水稻根生物量,但对水稻地上部生物量影响不显著。NPs能够诱导根表铁膜形成,然而铁膜量随着柠檬酸浓度增加而下降,可能是由于柠檬酸降低NPs的Fe2+释放量造成的;但是2.10 mg·L~(-1)柠檬酸包被NPs能显著提高根表铁膜量。根表铁膜主要以无定型为主(除柠檬酸包被处理外),晶格态仅占铁膜总量的24.88%~48.12%;其中,由于根表铁膜的晶格构造与NPs类似,可能晶格态铁膜主要来源于NPs的直接吸附沉淀。柠檬酸的加入显著降低Fe在根表和根中累积,但是增加了Fe在地上部的累积;然而,柠檬酸包被NPs处理能够增加Fe在根表和植株地上部的累积,但降低Fe在根系中的累积。2.10 mg·L~(-1)柠檬酸(包被和未包被NPs处理)能够减弱Fe从根表向根内的转移,但是增强了Fe从根向地上部的转移。不同NPs处理条件下,Fe在水稻植株不同部位均存在富集现象,根表和地上部的富集系数显著高于根内。     

溶胶凝胶法铁基载氧体的制备与反应性能研究

采用以金属醇盐和无机盐为前驱物的两种溶胶凝胶法,以Al2O3为惰性载体,制备了Fe2O3质量分数为70%的载氧体Fe2O3/Al2O3。X射线衍射分析(XRD)表明,载氧体主要成分为Fe2O3和Al2O3。X射线荧光光谱(XRF)证明,样品中Fe2O3/Al2O3含量与设计值接近;利用不同升温速率的程序升温还原(TPR-H2)测试发现,与商业氧化铁相比,溶胶凝胶法制备的载氧体反应峰向高温区移动,说明惰性载体Al2O3对反应活性的提高作用有限。利用同步热重分析仪(TGA)对载氧体进行循环周期测试,合成的载氧体较商业载氧体具有较高的传氧能力和还原反应速率,并且在循环周期内保持了良好的反应性能。说明惰性组分Al2O3通过优化载氧体物理结构,提高了反应过程热效应的稳定性,进一步加强了Fe2O3晶格氧持续、高效的反应活性。     

改性高铝水泥吸附除去水中氟的研究

采用静态吸附法研究了改性高铝水泥对含氟水的除氟性能,结果表明:用硫酸铝溶液0.5 mol/L浸泡高铝水泥8h制成改性高铝水泥,然后用其与含氟水震荡反应7 h,控制含氟水的pH在6~8范围内,能提高改性高铝水泥的吸附率,对含氟10 mg/g的溶液,此优化条件下的最大除氟率约96%。     

(111)晶面暴露的NiO纳米催化剂的制备及其CO催化氧化性能

采用溶剂热法,以Ni(NO_3)_3·6H_2O、均苯三甲酸以及N,N-二甲基甲酰胺(DMF)为原料快速合成金属有机骨架材料Ni_3(BTC)_2·12H_2O晶体。以Ni_3(BTC)_2·12H_2O为前体,通过焙烧得到具有(111)面的NiO颗粒用于CO催化氧化反应,并与由硝酸镍热解得到的NiO(R)催化剂进行对比。通过X射线衍射(XRD)、N_2物理吸附-脱附、透射电子显微镜(TEM)以及X射线光电子能谱(XPS)等方法对具有(111)面的NiO颗粒的组成、结构和形貌进行表征。CO催化氧化结果表明,具有(111)面的NiO颗粒的催化活性优于普通NiO催化剂的催化活性。     

土壤铝存在形式对马铃薯抵抗侵染软腐病菌的影响

[目的]从土壤化学角度探讨西北地区适合种植马铃薯的病理原因。[方法]通过模拟酸性及碱性土壤中铝的2种形式氯化铝(Al3+)和胶体铝(Al(OH)3),研究马铃薯块茎受软腐病菌侵染时土壤胶体态的铝对块茎过氧化氢积累及病程蛋白表达的影响。[结果]土壤铝的溶出直接导致马铃薯块茎切片细胞的死亡。马铃薯感染软腐病菌过程中,Al3+处理加速了马铃薯的感病,而Al(OH)3则延缓了马铃薯的感病。Al3+处理在加速马铃薯细胞死亡的同时产生大量的H2O2,而Al(OH)3在产生较高H2O2积累的同时并未造成明显的马铃薯细胞死亡。SDS-PAGE电泳分析表明,Al(OH)3处理的马铃薯明显不同于Al3+及空白对照。[结论]马铃薯块茎在感病过程中受土壤铝溶出率及铝形态变化的双重影响。     

0.2μm Al2O3陶瓷膜微滤清络通痹水提液的污染机制研究

[目的]探讨0.2μm Al2O3陶瓷膜微滤清络通痹水提液过程中的膜污染机制。[方法]以清络通痹组方水提液为研究对象,根据Darcy-Poiseuille定律确定过滤阻力分布情况,对污染膜表面和截面进行高分辨扫描电镜观测,同时对污染膜表面沉积层的组成物质进行了傅里叶变换红外光谱分析和粒径分析。[结果]阻力分布和SEM图结果显示：0.2μm Al2O3膜污染主要发生在膜表面。膜表面污染物主要是含C=O、CO-NH和C-O-C官能团的化学物质。表面污染物的粒径以体积百分数计主要集中在21.157μm左右;以数量计主要集中在0.596μm左右。[结论]研究微滤过程中的膜污染机制对于减缓膜通量减少及寻找有效的膜再生方法有重要指导意义。     

AlH2P3O10·2H2 O（Ⅰ）对水中Ni^2＋的吸附动力学和热力学研究

采用静态吸附法研究Al2O3-P2O5-H2O反应体系产物三聚磷酸二氢铝Ⅰ型二水物[AlH2P3O10.2H2O（Ⅰ）]吸附水中Ni2＋的动力学和热力学。考察了温度、浓度、粒径、pH和搅拌速度对吸附过程的影响,通过不同温度下的吸附等温热力学性能的变化,计算了吸附焓、吸附熵和自由能。结果表明,在试验范围内,AlH2P3O10.2H2O（Ⅰ）对Ni2＋的吸附符合Langmuir吸附等温方程式,过程受颗粒扩散控制,反应级数为1.88,298.15 K时的热力学数据为：Ea=11.561 kJ/mol,ΔH=35.75 kJ/mol,ΔS=190.58 J/（mol.K）,ΔG=-21.07 kJ/mol,吸附为自发的吸热过程,其吸附动力学总方程为：1-2/3x-（1-x）2/3=0.36r02C01.88exp（-11 561/RT）。     

The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts

One of the main stumbling blocks in developing rational design strategies for heterogeneous catalysis is that the complexity of the catalysts impairs efforts to characterize their active sites. We show how to identify the crucial atomic structure motif for the industrial Cu/ZnO/Al(2)O(3) methanol synthesis catalyst by using a combination of experimental evidence from bulk, surface-sensitive, and imaging methods collected on real high-performance catalytic systems in combination with density functional theory calculations. The active site consists of Cu steps decorated with Zn atoms, all stabilized by a series of well-defined bulk defects and surface species that need to be present jointly for the system to work.     

First occurrence of the garnet-ilmenite transition in silicates

Pyrope garnet (Mg(3)Al(2)Si(3)O(12)) has been found to transform to an ilmenite-type phase at a loading pressure between 240 and 250 kilobars and at about 1000 degrees to 1400 degrees C in a diamond-anvil press coupled with laser heating. The lattice parameters for the ilmenite-type phase of (Mg(.75) Al(.25))(Si(.75) Al(.25))O(3) are a(0) = 4.755 +/- 0.002 and c(0) = 13.360 +/- 0.005 angstroms. The zero-pressure volume change associated with the garnet-ilmenite transition is calculated to be -7.1 percent. This result verifies the prediction that pyrope garnet would transform to the ilmenite structure at high pressure first suggested in 1962 by Clark et al. and Ringwood.     

Structure of the ultrathin aluminum oxide film on NiAl(110)

The well-ordered aluminum oxide film formed by oxidation of the NiAl(110) surface is the most intensely studied metal surface oxide, but its structure was previously unknown. We determined the structure by extensive ab initio modeling and scanning tunneling microscopy experiments. Because the topmost aluminum atoms are pyramidally and tetrahedrally coordinated, the surface is different from all Al2O3 bulk phases. The film is a wide-gap insulator, although the overall stoichiometry of the film is not Al2O3 but Al10O13. We propose that the same building blocks can be found on the surfaces of bulk oxides, such as the reduced corundum (0001) surface.     

Exceptional activity for methane combustion over modular Pd@CeO2 subunits on functionalized Al2O3

There is a critical need for improved methane-oxidation catalysts to both reduce emissions of methane, a greenhouse gas, and improve the performance of gas turbines. However, materials that are currently available either have low activity below 400°C or are unstable at higher temperatures. Here, we describe a supramolecular approach in which single units composed of a palladium (Pd) core and a ceria (CeO(2)) shell are preorganized in solution and then homogeneously deposited onto a modified hydrophobic alumina. Electron microscopy and other structural methods revealed that the Pd cores remained isolated even after heating the catalyst to 850°C. Enhanced metal-support interactions led to exceptionally high methane oxidation, with complete conversion below 400°C and outstanding thermal stability under demanding conditions.     

Creep-resistant, Al2O3-forming austenitic stainless steels

A family of inexpensive, Al2O3-forming, high-creep strength austenitic stainless steels has been developed. The alloys are based on Fe-20Ni-14Cr-2.5Al weight percent, with strengthening achieved through nanodispersions of NbC. These alloys offer the potential to substantially increase the operating temperatures of structural components and can be used under the aggressive oxidizing conditions encountered in energy-conversion systems. Protective Al2O3 scale formation was achieved with smaller amounts of aluminum in austenitic alloys than previously used, provided that the titanium and vanadium alloying additions frequently used for strengthening were eliminated. The smaller amounts of aluminum permitted stabilization of the austenitic matrix structure and made it possible to obtain excellent creep resistance. Creep-rupture lifetime exceeding 2000 hours at 750 degrees C and 100 megapascals in air, and resistance to oxidation in air with 10% water vapor at 650 degrees and 800 degrees C, were demonstrated.