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   

Oxygen-mediated diffusion of oxygen vacancies on the TiO2(110) surface

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.     

The role of interstitial sites in the Ti3d defect state in the band gap of titania

Titanium dioxide (TiO2) has a number of uses in catalysis, photochemistry, and sensing that are linked to the reducibility of the oxide. Usually, bridging oxygen (Obr) vacancies are assumed to cause the Ti3d defect state in the band gap of rutile TiO2(110). From high-resolution scanning tunneling microscopy and photoelectron spectroscopy measurements, we propose that Ti interstitials in the near-surface region may be largely responsible for the defect state in the band gap. We argue that these donor-specific sites play a key role in and may dictate the ensuing surface chemistry, such as providing the electronic charge required for O2 adsorption and dissociation. Specifically, we identified a second O2 dissociation channel that occurs within the Ti troughs in addition to the O2 dissociation channel in O(br) vacancies. Comprehensive density functional theory calculations support these experimental observations.     

Electronic structure and valence-bond band structure of cuprate superconducting materials

From ab initio calculations on various clusters representing the La2-xSrxCu(1)O(4) and Y(1)Ba(2)Cu(3)O(7) classes of high-temperature superconductors, it is shown that (i) all copper sites have a Cu(II)(d(9))oxidation state with one unpaired spin that is coupled antiferromagnetically to the spins of adjacent Cu(II) sites; (ii) oxidation beyond the cupric (Cu(II)) state leads not to Cu(III) but rather to oxidized oxygen atoms, with an oxygen ppi hole bridging two Cu(II) sites; (iii) the oxygen ppihole at these oxidized sites is ferromagnetically coupled to the adjacent Cu(II)d electrons despite the fact that this is opposed by the direct dd exchange; and (iv) the hopping of these oxygen ppi holes (in CuO sheets or chains) from site to site is responsible for the conductivity in these systems (N-electron band structures are reported for the migration of these localized charges).     

Electron transfer-induced dynamics of oxygen molecules on the TiO2(110) surface

Diffusion of oxygen molecules on transition metal oxide surfaces plays a vital role for the understanding of catalysis and photocatalysis on these materials. By means of time-resolved scanning tunneling microscopy, we provide evidence for a charge transfer-induced diffusion mechanism for O2 molecules adsorbed on a rutile TiO2(110) surface. The O2 hopping rate depended on the number of surface donors (oxygen vacancies), which determines the density of conduction band electrons. These results may have implications for the understanding of oxidation processes on metal oxides in general.     

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.     

The Exclusion of D2O from the Hydration Sphere of FeSO4{middle dot} 7H2O Oxidized by Thiobacillus ferrooxidans

Infrared spectra demonstrate that neither FeSO(4) . 7H(2)O nor its bacterial or abiotic hydrated oxidation products incorporate deuterium in acid D(2)O solutions. Deuterium exchange occurred as bridging OD when bacterially oxidized iron was precipitated from D(2)O solutions as ferric hydroxysulfates. The exclusion of deuterium depended upon the stabilization of aquated Fe(II) and Fe(III) complexes by sulfate ions in outer-sphere coordination and is consistent with the requirement and postulated role of sulfate in iron oxidation by Thiobacillus ferrooxidans.     

Solvent-free oxidation of primary carbon-hydrogen bonds in toluene using Au-Pd alloy nanoparticles

Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO(2) are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO(2) supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites.     

Scanning tunneling microscopy of galena (100) surface oxidation and sorption of aqueous gold

Scanning tunneling microscopy was used to characterize the growth of oxidized areas on galena (100) surfaces and the formation of gold islands by the reductive adsorption of AuCl(4)(-) from aqueous solution. The gold islands and galena substrate were distinguished by atomic resolution imaging and tunneling spectroscopy. Oxidized areas on galena have [110]-trending boundaries; gold islands elongate along [110] directions. However, there are no obvious structural registry considerations that would lead to elongation of gold islands in a [110] direction. Instead, it is probable that a direct coupling of gold reduction and sulfide surface oxidation controls the initial formation of gold islands. Gold islands grow less quickly on preoxidized galena surfaces and show no preferred direction of growth.     

Atomic-scale structure and catalytic reactivity of the RuO(2)(110) surface

The structure of RuO(2)(110) and the mechanism for catalytic carbon monoxide oxidation on this surface were studied by low-energy electron diffraction, scanning tunneling microscopy, and density-functional calculations. The RuO(2)(110) surface exposes bridging oxygen atoms and ruthenium atoms not capped by oxygen. The latter act as coordinatively unsaturated sites-a hypothesis introduced long ago to account for the catalytic activity of oxide surfaces-onto which carbon monoxide can chemisorb and from where it can react with neighboring lattice-oxygen to carbon dioxide. Under steady-state conditions, the consumed lattice-oxygen is continuously restored by oxygen uptake from the gas phase. The results provide atomic-scale verification of a general mechanism originally proposed by Mars and van Krevelen in 1954 and are likely to be of general relevance for the mechanism of catalytic reactions at oxide surfaces.     

A cytochrome C oxidase model catalyzes oxygen to water reduction under rate-limiting electron flux

We studied the selectivity of a functional model of cytochrome c oxidase's active site that mimics the coordination environment and relative locations of Fe(a3), Cu(B), and Tyr(244). To control electron flux, we covalently attached this model and analogs lacking copper and phenol onto self-assembled monolayer-coated gold electrodes. When the electron transfer rate was made rate limiting, both copper and phenol were required to enhance selective reduction of oxygen to water. This finding supports the hypothesis that, during steady-state turnover, the primary role of these redox centers is to rapidly provide all the electrons needed to reduce oxygen by four electrons, thus preventing the release of toxic partially reduced oxygen 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.     

An inducible endothelial cell surface glycoprotein mediates melanoma adhesion

Hematogenous metastasis requires the arrest and extravasation of blood-borne tumor cells, possibly involving direct adhesive interactions with vascular endothelium. Cytokine activation of cultured human endothelium increases adhesion of melanoma and carcinoma cell lines. An inducible 110-kD endothelial cell surface glycoprotein, designated INCAM-110, appears to mediate adhesion of melanoma cells. In addition, an inducible endothelial receptor for neutrophils, ELAM-1, supports the adhesion of a human colon carcinoma cell line. Thus, activation of vascular endothelium in vivo that results in increased expression of INCAM-110 and ELAM-1 may promote tumor cell adhesion and affect the incidence and distribution of metastases.     

Antiarthritic gold compounds effectively quench electronically excited singlet oxygen

Although certain gold [Au(I)] compounds have been used effectively in the treatment of rheumatoid arthritis for some years, the molecular basis for such therapeutic action has been unclear. One possible mechanism of the action of Au(I) compounds is that they protect unsaturated membrane lipids and proteins against oxidative degradation caused by activated phagocytes that are not properly regulated. In this study it has been shown that superoxide ion (O-2.), a product of activated phagocytes, can be oxidized to electronically excited singlet oxygen (O1(2)delta g), an agent that is capable of peroxidation of unsaturated fatty acid derivatives. It has also been shown that antiarthritic Au(I) compounds are effective deactivators of O1(2)delta g with quenching constants on the order of 10(7) M-1 sec-1.     

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.     

X-ray Detection of the Period-Four Cycling of the Manganese Cluster in Photosynthetic Water Oxidizing Enzyme

X-ray absorption near-edge structure spectra of the manganese (Mn) cluster in physiologically native intermediate states of photosynthetic water oxidation induced by short laser flash were measured with a compact heat-insulated chamber equipped with an x-ray detector near the sample surface. The half-height energy of the Mn Kedge showed a period-four oscillation dependent on cycling of the Joliot-Kok's oxygen clock. The flash number-dependent shift in the Mn K-edge suggests that the Mn cluster is oxidized by one electron upon the S(0)-to-S(1), S(1)-to-S(2), and S(2)-to-S(3) transitions and then reduced upon the S(3)-to-S(0) transition that releases molecular oxygen.     

Activity of CeOx and TiOx nanoparticles grown on Au(111) in the water-gas shift reaction

The high performance of Au-CeO2 and Au-TiO2 catalysts in the water-gas shift (WGS) reaction (H2O + CO-->H2 + CO2) relies heavily on the direct participation of the oxide in the catalytic process. Although clean Au(111) is not catalytically active for the WGS, gold surfaces that are 20 to 30% covered by ceria or titania nanoparticles have activities comparable to those of good WGS catalysts such as Cu(111) or Cu(100). In TiO(2-x)/Au(111) and CeO(2-x)/Au(111), water dissociates on O vacancies of the oxide nanoparticles, CO adsorbs on Au sites located nearby, and subsequent reaction steps take place at the metal-oxide interface. In these inverse catalysts, the moderate chemical activity of bulk gold is coupled to that of a more reactive oxide.     

Hydrated electron dynamics: from clusters to bulk

The electronic relaxation dynamics of size-selected (H2O)n-/(D2O)n[25 eaq-(s(dagger)) internal conversion lifetime.     

氧化羊骨油对羊肉味调味基料挥发性风味物质的影响

【目的】确定添加适度氧化的羊骨油对热反应型羊肉味调味基料挥发性风味物质的影响,为高品质羊肉味调味基料风味的开发提供理论依据。【方法】评价以过氧化值、酸价和茴香胺值表征的氧化羊骨油对调味基料挥发性风味物质的影响,利用Pen3型电子鼻对不添加羊骨油、添加未氧化羊骨油和添加适度氧化羊骨油的3个热反应体系进行研究,以电子鼻主成分分析中的区分指数作为检测指标,确定3个热反应体系的区分度;应用固相微萃取-气质联用技术分离鉴定基料的挥发性风味物质,通过“相对气味活度值(ROAV)”评价各挥发性风味物质对调味基料总体风味的贡献,并结合聚类分析方法,确定添加氧化羊骨油后羊肉味调味基料的关键挥发性风味物质。【结果】电子鼻结果显示,未添加羊骨油与添加未氧化羊骨油的调味基料间区别指数为0.589,未添加羊骨油与添加氧化羊骨油的调味基料间区分指数为0.917,添加未氧化羊骨油与添加氧化羊骨油的调味基料间区分指数为0.787。气质联用结果显示,不添加羊骨油、添加未氧化羊骨油和添加适度氧化羊骨油的3组调味基料中挥发性风味物质的种类分别为42种、63种和61种,主要为醛类、烃类;在添加未氧化羊骨油组和添加氧化羊骨油组中,含硫、含氮杂环化合物的相对含量差异不显著,而对调味料风味改善贡献较小的烃类物质相对含量显著降低,同时醛类物质的相对含量显著增加,添加羊骨油尤其是氧化羊骨油可使热反应体系生成更多的醛类挥发性风味物质;确定3组调味基料中关键挥发性物质(ROAV≥1)有11种：辛醛、壬醛、癸醛、反,反-2,4-癸二烯醛、桃醛、庚醛、反-2-壬烯醛、十二醛、1-辛烯-3-醇、庚醇、反,反-2,4-壬二烯醛,这些关键挥发性物质主要以脂肪香气为主,并包含甜香、青香、焦香和柑橘等香气;通过聚类分析将11种关键风味物质分为三类,第一类物质在添加氧化羊骨油后ROAV值变化较小;第二类包括反,反-2,4-癸二烯醛、反-2-壬烯醛,在添加氧化羊骨油后ROAV值显著增加;第三类为癸醛,在添加氧化羊骨油后ROAV值显著降低,而第二类与第三类物质在未添加羊骨油组和添加未氧化羊骨油组间的差异不显著（P >0.05）。【结论】添加氧化羊骨油,可以显著影响羊肉味调味基料挥发性风味物质的种类,增强热反应型羊肉味调味基料的风味,反,反-2,4-癸二烯醛与反-2-壬烯醛是改善调味基料最关键挥发性风味物质。     

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