Laminar growth of ultrathin metal films on metal oxides: Co on hydroxylated alpha-Al2O3(0001)

Metals deposited in vacuum on metal oxides such as alumina normally grow as three-dimensional clusters because of weak adatom-substrate interactions. This tendency hinders our ability to form interfaces of ultrathin, laminar metal films on oxides for use in microelectronics and other technologies where nanostructural control is desired. We present experimental and theoretical results showing that room temperature Co deposition on fully hydroxylated clean sapphire (alpha-Al2O3) produces a surface chemical reaction that leads to laminar growth, despite a large mismatch in lattice constants. This process should be applicable to a wide range of metals and metal oxides.     

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.     

Wet electrons at the H2O/TiO2(110) surface

At interfaces of metal oxide and water, partially hydrated or "wet-electron" states represent the lowest energy pathway for electron transfer. We studied the photoinduced electron transfer at the H2O/TiO2(110) interface by means of time-resolved two-photon photoemission spectroscopy and electronic structure theory. At approximately 1-monolayer coverage of water on partially hydroxylated TiO2 surfaces, we found an unoccupied electronic state 2.4 electron volts above the Fermi level. Density functional theory shows this to be a wet-electron state analogous to that reported in water clusters and which is distinct from hydrated electrons observed on water-covered metal surfaces. The decay of electrons from the wet-electron state to the conduction band of TiO2 occurs in 相似文献   

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).     

Atomic Control of the SrTiO3 Crystal Surface

The atomically smooth SrTiO(3) (100) with steps one unit cell in height was obtained by treating the crystal surface with a pH-controlled NH(4)F-HF solution. The homoepitaxy of SrTiO(3) film on the crystal surface proceeds in a perfect layer-by-layer mode as verified by reflection high-energy electron diffraction and atomic force microscopy. Ion scattering spectroscopy revealed that the TiO(2) atomic plane terminated the as-treated clean surface and that the terminating atomic layer could be tuned to the SrO atomic plane by homooepitaxial growth. This technology provides a well-defined substrate surface for atomically regulated epitaxial growth of such perovskite oxide films as YBa(2)Cu(3)O(7-delta).     

Boron-Oxygen Polyanion in the Crystal Structure of Tunellite

The crystal structure of tunellite, SrO.3B(2)O(3).4H(2)O, with infinite sheets of composition n[B(6)O(9)(OH)(2)](2-), has cations and water molecules in the spaces within the sheets. Adjacent sheets are held together by hydrogen bonding through the water molecules. The boron-oxygen polyanions provide the first example in hydrated borate crystals of one oxygen linked to three borons.     

Kinetic evidence for five-coordination in AlOH(aq)2+ ion

Trivalent aluminum ions are important in natural bodies of water, but the structure of their coordination shell is a complex unsolved problem. In strong acid (pH < 3.0), Al(III) exists almost entirely as the octahedral Al(H2O)6(3+) ion, whereas in basic conditions (pH > 7), a tetrahedral Al(OH)(4- structure prevails. In the biochemically and geochemically critical pH range of 4.3 to 7.0, the ion structures are less clear. Other hydrolytic species, such as AlOH(aq)2+, exist and are traditionally assumed to be hexacoordinate. We show, however, that the kinetics of proton and water exchange on aqueous Al(III), coupled with Car-Parrinello simulations, support a five-coordinate Al(H2O)4OH2+ ion as the predominant form of AlOH(aq)2+ under ambient conditions. This result contrasts Al(III) with other trivalent metal aqua ions, for which there is no evidence for stable pentacoordinate hydrolysis products.     

Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability

The slow rate of the oxygen reduction reaction (ORR) in the polymer electrolyte membrane fuel cell (PEMFC) is the main limitation for automotive applications. We demonstrated that the Pt3Ni(111) surface is 10-fold more active for the ORR than the corresponding Pt(111) surface and 90-fold more active than the current state-of-the-art Pt/C catalysts for PEMFC. The Pt3Ni(111) surface has an unusual electronic structure (d-band center position) and arrangement of surface atoms in the near-surface region. Under operating conditions relevant to fuel cells, its near-surface layer exhibits a highly structured compositional oscillation in the outermost and third layers, which are Pt-rich, and in the second atomic layer, which is Ni-rich. The weak interaction between the Pt surface atoms and nonreactive oxygenated species increases the number of active sites for O2 adsorption.     

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。     

Observation of large water-cluster anions with surface-bound excess electrons

Anionic water clusters have long been studied to infer properties of the bulk hydrated electron. We used photoelectron imaging to characterize a class of (H2O)n- and (D2O)n- cluster anions (n 相似文献   

Nonstoichiometric dislocation cores in alpha-alumina

Little is known about dislocation core structures in oxides, despite their central importance in controlling electrical, optical, and mechanical properties. It has often been assumed, on the basis of charge considerations, that a nonstoichiometric core structure could not exist. We report atomic-resolution images that directly resolve the cation and anion sublattices in alumina (alpha-Al2O3). A dissociated basal edge dislocation is seen to consist of two cores; an aluminum column terminates one partial, and an oxygen column terminates the second partial. Each partial core is locally nonstoichiometric due to the excess of aluminum or oxygen at the core. The implication for mechanical properties is that the mobile high-temperature dislocation core structure consists of two closely spaced partial dislocations. For basal slip to occur, synchronized motion of the partials on adjacent planes is required.     

High-density electron anions in a nanoporous single crystal: [Ca24Al28O64]4+(4e-)

We removed approximately 100% of clathrated oxygen ions from the crystallographic cages in a single crystal of 12CaO.7Al2O3, leading to the formation of high-density (approximately 2 x 10(21) cm-3) electrons highly localized in the cages. The resulting electron forms a structure that we interpret as an F+ center and migrates throughout the crystal by hopping to a neighboring cage with conductivity approximately 100 siemens per centimeter, demonstrating that the encaged electron behaves as an anion. The electron anions couple antiferromagnetically with each other, forming a diamagnetic pair or singlet bipolaron. The resulting [Ca24Al28O64]4+(4e-) may be regarded as a thermally and chemically stable single crystalline "electride."     

Enhanced bonding of gold nanoparticles on oxidized TiO2(110)

We studied the nucleation of gold clusters on TiO2(110) surfaces in three different oxidation states by high-resolution scanning tunneling microscopy. The three TiO2(110) supports chosen were (i) reduced (having bridging oxygen vacancies), (ii) hydrated (having bridging hydroxyl groups), and (iii) oxidized (having oxygen adatoms). At room temperature, gold nanoclusters nucleate homogeneously on the terraces of the reduced and oxidized supports, whereas on the hydrated TiO2(110) surface, clusters form preferentially at the step edges. From interplay with density functional theory calculations, we identified two different gold-TiO2(110) adhesion mechanisms for the reduced and oxidized supports. The adhesion of gold clusters is strongest on the oxidized support, and the implications of this finding for catalytic applications are discussed.     

Calorimetric measurement of the energy difference between two solid surface phases

A recently designed single-crystal surface calorimeter has been deployed to measure the energy difference between two solid surface structures. The clean Pt{100} surface is reconstructed to a stable phase in which the surface layer of platinum atoms has a quasi-hexagonal structure. By comparison of the heats of adsorption of CO and of C(2)H(4) on this stable Pt{100}-hex phase with those on a metastable Pt{100}-(1x1) surface, the energy difference between the two clean phases was measured as 20 +/- 3 and 25 +/- 3 kilojoules per mole of surface platinum atoms.     

海南岛火山岩砖红壤铁质风化壳主量元素特征[1]

通过对海南岛西北部火山岩砖红壤铁质风化壳剖面样品进行X荧光光谱法检测、风化特征指数及质量迁移系数的计算，揭示海南岛新生代火山岩砖红壤铁质风化壳的主量元素分布、风化强度和迁移特征。风化壳主量元素以Fe2O3、Al2O3、SiO2为主，K、Na、Ca、Mg等易溶组分较低；Fe2O3、Al2O3富集、SiO2淋失的热带地区风化特征。风化层CIA指数高达95%以上、Fe2O3/Al2O3上升，BA值较低， SiO2/Al2O3、SiO2/R2O3、BA下降；以Zr为参比元素，铁、铝迁移系数大于1，最大可达4.029，钠、钾、钙、镁、硅、锰迁移系数小于1，可低至-0.996。研究认为海南岛西北部火山岩风化壳表现为典型的脱硅富铁，铁质元素强烈富集，其它元素淋失明显，且铁铝元素发生了的分异，是比较成熟的风化壳。     

MgB2 superconducting thin films with a transition temperature of 39 kelvin

We fabricated high-quality c axis-oriented epitaxial MgB2 thin films using a pulsed laser deposition technique. The thin films grown on (1 i 0 2) Al2O3 substrates have a transition temperature of 39 kelvin. The critical current density in zero field is approximately 6 x 10(6) amperes per cubic centimeter at 5 kelvin and approximately 3 x 10(5) amperes per cubic centimeter at 35 kelvin, which suggests that this compound has potential for electronic device applications, such as microwave devices and superconducting quantum interference devices. For the films deposited on Al2O3, x-ray diffraction patterns indicate a highly c axis-oriented crystal structure perpendicular to the substrate surface.     

Direct imaging of reconstructed atoms on TiO2 (110) surfaces

Determining the atomic structures of oxide surfaces is critical for understanding their physical and chemical properties but also challenging because the breaking of atomic bonds in the formation of the surface termination can involve complex reconstructions. We used advanced transmission electron microscopy to directly observe the atomic structure of reduced titania (TiO2) (110) surfaces from directions parallel to the surface. In our direct atomic-resolution images, reconstructed titanium atoms at the top surface layer are clearly imaged and are found to occupy the interstitial sites of the TiO2 structure. Combining observations from two orthogonal directions, the three-dimensional positioning of the Ti interstitials is identified at atomic dimensions and allows a resolution of two previous models that differ in their oxygen stoichiometries.     

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。     

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。     

Electrons in finite-sized water cavities: hydration dynamics observed in real time

We directly observed the hydration dynamics of an excess electron in the finite-sized water clusters of (H2O)n- with n = 15, 20, 25, 30, and 35. We initiated the solvent motion by exciting the hydrated electron in the cluster. By resolving the binding energy of the excess electron in real time with femtosecond resolution, we captured the ultrafast dynamics of the electron in the presolvated ("wet") and hydrated states and obtained, as a function of cluster size, the subsequent relaxation times. The solvation time (300 femtoseconds) after the internal conversion [140 femtoseconds for (H2O)35-] was similar to that of bulk water, indicating the dominant role of the local water structure in the dynamics of hydration. In contrast, the relaxation in other nuclear coordinates was on a much longer time scale (2 to 10 picoseconds) and depended critically on cluster size.