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1.
Knowing the thermodynamic stability of transition metal oxide nanoparticles is important for understanding and controlling their role in a variety of industrial and environmental systems. Using calorimetric data on surface energies for cobalt, iron, manganese, and nickel oxide systems, we show that surface energy strongly influences their redox equilibria and phase stability. Spinels (M(3)O(4)) commonly have lower surface energies than metals (M), rocksalt oxides (MO), and trivalent oxides (M(2)O(3)) of the same metal; thus, the contraction of the stability field of the divalent oxide and expansion of the spinel field appear to be general phenomena. Using tabulated thermodynamic data for bulk phases to calculate redox phase equilibria at the nanoscale can lead to errors of several orders of magnitude in oxygen fugacity and of 100 to 200 kelvin in temperature. 相似文献
2.
Schaub R Wahlström E Rønnau A Lagsgaard E Stensgaard I Besenbacher F 《Science (New York, N.Y.)》2003,299(5605):377-379
Defects such as oxygen vacancies play a crucial role in the surface properties of transition metal oxides. By means of time-resolved, high-resolution scanning tunneling microscopy, we unraveled an adsorbate-mediated diffusion mechanism of oxygen vacancies on rutile TiO2(110). Adsorbed oxygen molecules mediate vacancy diffusion through the loss of an oxygen atom to a vacancy and the sequential capture of an oxygen atom from a neighboring bridging oxygen row, leading to an anisotropic oxygen vacancy diffusion pathway perpendicular to the bridging oxygen rows. 相似文献
3.
Eng PJ Trainor TP Brown GE Waychunas GA Newville M Sutton SR Rivers ML 《Science (New York, N.Y.)》2000,288(5468):1029-1033
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. 相似文献
4.
Anderson TM Neiwert WA Kirk ML Piccoli PM Schultz AJ Koetzle TF Musaev DG Morokuma K Cao R Hill CL 《Science (New York, N.Y.)》2004,306(5704):2074-2077
Terminal mono-oxo complexes of the late transition metal elements have long been considered too unstable to synthesize because of repulsion between the oxygen electrons and the mostly filled metal d orbitals. A platinum(IV)-oxo compound flanked by two polytungstate ligands, K7Na9[O=Pt(H2O)L2], L = [PW9O34(9-)], has now been prepared and isolated at room temperature as air-stable brown crystals. X-ray and neutron diffraction at 30 kelvin revealed a very short [1.720(18) angstrom] Pt-O bond and no evidence of a hydrogen atom at the terminal oxygen, ruling out a better precedented Pt-OH complex. Density functional theory and spectroscopic data account for the stability of the Pt(IV)-oxo unit by electron withdrawal into delocalized orbitals of the polytungstates. 相似文献
5.
Clark JR 《Science (New York, N.Y.)》1963,141(3586):1178-1179
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. 相似文献
6.
Tunneling electrons from the tip of a scanning tunneling microscope were used to induce and monitor the reversible rotation of single molecules of molecular oxygen among three equivalent orientations on the platinum(111) surface. Detailed studies of the rotation rates indicate a crossover from a single-electron process to a multielectron process below a threshold tunneling voltage. Values for the energy barrier to rotation and the vibrational relaxation rate of the molecule were obtained by comparing the experimental data with a theoretical model. The ability to induce the controlled motion of single molecules enhances our understanding of basic chemical processes on surfaces and may lead to useful single-molecule devices. 相似文献
7.
采用第一性原理的密度泛函理论计算了O原子在Rh（100）表面的吸附,得到了电子特性及各种结构参数,并给出了不同覆盖度下O原子在Rh（100）表面上3个位置吸附后的能量,结果表明,O原子在Rh（100）表面可以发生稳定的吸附,最高吸附能为2．53eV。同时,通过对O原子的态密度进行分析,得到如下结论：O原子在Rh（100）面上的吸附主要是由于O的2p轨道与基底金属的4d轨道相互作用的结果。 相似文献
8.
Many of the early transition elements form large polynuclear metal-oxygen anions containing up to 200 atoms or more. Although these polyoxoanions have been investigated for more than a century, detailed studies of structure and reactivity were not possible until the development of modern x-ray crystallographic and nuclear magnetic resonance spectroscopic techniques. Systematic studies of small polyoxoanions in inert, aprotic solvents have clarified many of the principles governing their structure and reactivity, and also have made possible the preparation of entirely new types of covalent derivatives such as CH(2)Mo(4)O(15)H(3-), C(5)H(5)TiMo(5)O(18)(3-), and (OC)(3)Mn(Nb(2)W(4)O(19))(3-). Since most early transition metal polyoxoanions have structures based on close-packed oxygen arrays containing interstitial metal centers, their chemistry offers a rare opportunity to study chemical transformations in detail on well-defined metal oxide surfaces. 相似文献
9.
The selective oxidation of alcohols in aqueous phase over supported metal catalysts is facilitated by high-pH conditions. We have studied the mechanism of ethanol and glycerol oxidation to acids over various supported gold and platinum catalysts. Labeling experiments with (18)O(2) and H(2)(18)O demonstrate that oxygen atoms originating from hydroxide ions instead of molecular oxygen are incorporated into the alcohol during the oxidation reaction. Density functional theory calculations suggest that the reaction path involves both solution-mediated and metal-catalyzed elementary steps. Molecular oxygen is proposed to participate in the catalytic cycle not by dissociation to atomic oxygen but by regenerating hydroxide ions formed via the catalytic decomposition of a peroxide intermediate. 相似文献
10.
Esch F Fabris S Zhou L Montini T Africh C Fornasiero P Comelli G Rosei R 《Science (New York, N.Y.)》2005,309(5735):752-755
The high performance of ceria (CeO2) as an oxygen buffer and active support for noble metals in catalysis relies on an efficient supply of lattice oxygen at reaction sites governed by oxygen vacancy formation. We used high-resolution scanning tunneling microscopy and density functional calculations to unravel the local structure of surface and subsurface oxygen vacancies on the (111) surface. Electrons left behind by released oxygen localize on cerium ions. Clusters of more than two vacancies exclusively expose these reduced cerium ions, primarily by including subsurface vacancies, which therefore play a crucial role in the process of vacancy cluster formation. These results have implications for our understanding of oxidation processes on reducible rare-earth oxides. 相似文献
11.
Winther-Jensen B Winther-Jensen O Forsyth M Macfarlane DR 《Science (New York, N.Y.)》2008,321(5889):671-674
The air electrode, which reduces oxygen (O2), is a critical component in energy generation and storage applications such as fuel cells and metal/air batteries. The highest current densities are achieved with platinum (Pt), but in addition to its cost and scarcity, Pt particles in composite electrodes tend to be inactivated by contact with carbon monoxide (CO) or by agglomeration. We describe an air electrode based on a porous material coated with poly(3,4-ethylenedioxythiophene) (PEDOT), which acts as an O2 reduction catalyst. Continuous operation for 1500 hours was demonstrated without material degradation or deterioration in performance. O2 conversion rates were comparable with those of Pt-catalyzed electrodes of the same geometry, and the electrode was not sensitive to CO. Operation was demonstrated as an air electrode and as a dissolved O2 electrode in aqueous solution. 相似文献
12.
Relation between long-term trends of oxygen-18 isotope composition of precipitation and climate 总被引：1，自引：0，他引：1
Stable isotope ratios of oxygen ((18)O/(16)O) and hydrogen (D/H) in water have long been considered powerful indicators of paleoclimate. However, quantitative interpretation of isotope variations in terms of climate changes is hampered by a limited understanding of physical processes controlling the global isotope behavior. Analysis was conducted of time series of (18)O content (delta (18)O) of monthly precipitation and surface air temperature available through the International Atomic Energy Agency-World Meteorological Organization global network, "Isotopes in Precipitation." This study indicates that long-term changes of isotopic composition of precipitation over mid-and high-latitude regions during the past three decades closely followed long-term changes of surface air temperature with the average 8180-temperature coefficient around 0.6 per mil per degree Celsius. 相似文献
13.
Mao WL Mao HK Meng Y Eng PJ Hu MY Chow P Cai YQ Shu J Hemley RJ 《Science (New York, N.Y.)》2006,314(5799):636-638
When subjected to high pressure and extensive x-radiation, water (H2O) molecules cleaved, forming O-O and H-H bonds. The oxygen (O) and hydrogen (H) framework in ice VII was converted into a molecular alloy of O2 and H2. X-ray diffraction, x-ray Raman scattering, and optical Raman spectroscopy demonstrated that this crystalline solid differs from previously known phases. It remained stable with respect to variations in pressure, temperature, and further x-ray and laser exposure, thus opening new possibilities for studying molecular interactions in the hydrogen-oxygen binary system. 相似文献
14.
Dulub O Batzilln M Solovev S Loginova E Alchagirov A Madey TE Diebold U 《Science (New York, N.Y.)》2007,317(5841):1052-1056
When low-energy electrons strike a titanium dioxide surface, they may cause the desorption of surface oxygen. Oxygen vacancies that result from irradiating a TiO2(011)-2x1 surface with electrons with an energy of 300 electron volts were analyzed by scanning tunneling microscopy. The cross section for desorbing oxygen from the pristine surface was found to be 9 (+/-6) x 10(-17) square centimeters, which means that the initial electronic excitation was converted into atomic motion with a probability near unity. Once an O vacancy had formed, the desorption cross sections for its nearest and next-nearest oxygen neighbors were reduced by factors of 100 and 10, respectively. This site-specific desorption probability resulted in one-dimensional arrays of oxygen vacancies. 相似文献
15.
Kresse G Schmid M Napetschnig E Shishkin M Köhler L Varga P 《Science (New York, N.Y.)》2005,308(5727):1440-1442
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. 相似文献
16.
Singlet oxygen (1O2) is a highly reactive species formed through solar irradiation of organic matter in environmental waters. Implicated in a range of reactions, it has proven difficult to quantify its spatial distribution in natural waters. We assessed the microheterogeneous distribution of 1O2 in irradiated solutions containing chromophoric dissolved organic matter (CDOM) by using molecular probes of varying hydrophobicity. The apparent 1O2 concentrations ([1O2]app), measured by recently developed hydrophobic trap-and-trigger chemiluminescent probe molecules, were orders of magnitude higher than those measured by the conventional hydrophilic probe molecule furfuryl alcohol. The differential [1O2]app values measured by these probes reflect a steep concentration gradient between the CDOM macromolecules and the aqueous phase. A detailed kinetic model based on the data predicts probabilistic 1O2 distributions under different solvent conditions. 相似文献
17.
Vibrational studies that selectively probe molecular structure at CCl4/H2O and hydrocarbon/H2O interfaces show that the hydrogen bonding between adjacent water molecules at these interfaces is weak, in contrast to generally accepted models of water next to fluid hydrophobic surfaces that suggest strong hydrogen bonding. However, interactions between these water molecules and the organic phase result in substantial orientation of these weakly hydrogen-bonded water molecules in the interfacial region. The results have important implications for understanding water adjacent to hydrophobic surfaces and the penetration of water into hydrophobic phases. 相似文献
18.
We report a synthetic material, [Co2(bipy)3(SO4)2(H2O)2](bipy) (CH3OH), (1, where bipy = 4,4'-bipyridyl) that contains discrete reactive and inert structural motifs that undergo a reversible substitution reaction involving the concerted and spatially controlled introduction of bipyridine and methanol molecules at the reactive sites. This reaction defines the pore geometry of the resulting open-framework structure and controls the manner in which this structure sorbs small molecules. The molecules involved in the reaction are positioned by an array of well-defined interactions during their path to binding to the metal centers. 相似文献
19.
Corso M Auwärter W Muntwiler M Tamai A Greber T Osterwalder J 《Science (New York, N.Y.)》2004,303(5655):217-220
A highly regular mesh of hexagonal boron nitride with a 3-nanometer periodicity and a 2-nanometer hole size was formed by self-assembly on a Rh(111) single crystalline surface. Two layers of mesh cover the surface uniformly after high-temperature exposure of the clean rhodium surface to borazine (HBNH)3. The two layers are offset in such a way as to expose a minimum metal surface area. Hole formation is likely driven by the lattice mismatch of the film and the rhodium substrate. This regular nanostructure is thermally very stable and can serve as a template to organize molecules, as is exemplified by the decoration of the mesh by C60 molecules. 相似文献
20.
I Zeljkovic Z Xu J Wen G Gu RS Markiewicz JE Hoffman 《Science (New York, N.Y.)》2012,337(6092):320-323
High-temperature cuprate superconductors display unexpected nanoscale inhomogeneity in essential properties such as pseudogap energy, Fermi surface, and even superconducting critical temperature. Theoretical explanations for this inhomogeneity have ranged from chemical disorder to spontaneous electronic phase separation. We extend the energy range of scanning tunneling spectroscopy on Bi(2+y)Sr(2-y)CaCu(2)O(8+x), allowing a complete mapping of two types of interstitial oxygen dopants and vacancies at the apical oxygen site. We show that the nanoscale spatial variations in the pseudogap states are correlated with disorder in these dopant concentrations, particularly that of apical oxygen vacancies. 相似文献