Metal oxide chemistry in solution: the early transition metal polyoxoanions

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.     

The Resonating Valence Bond State in La2CuO4 and Superconductivity

The oxide superconductors, particularly those recently discovered that are based on La(2)CuO(4), have a set of peculiarities that suggest a common, unique mechanism: they tend in every case to occur near a metal-insulator transition into an odd-electron insulator with peculiar magnetic properties. This insulating phase is proposed to be the long-sought "resonating-valence-bond" state or "quantum spin liquid" hypothesized in 1973. This insulating magnetic phase is favored by low spin, low dimensionality, and magnetic frustration. The preexisting magnetic singlet pairs of the insulating state become charged superconducting pairs when the insulator is doped sufficiently strongly. The mechanism for superconductivity is hence predominantly electronic and magnetic, although weak phonon interactions may favor the state. Many unusual properties are predicted, especially of the insulating state.     

Ionic liquid-mediated selective conversion of CO₂ to CO at low overpotentials

Electroreduction of carbon dioxide (CO(2))--a key component of artificial photosynthesis--has largely been stymied by the impractically high overpotentials necessary to drive the process. We report an electrocatalytic system that reduces CO(2) to carbon monoxide (CO) at overpotentials below 0.2 volt. The system relies on an ionic liquid electrolyte to lower the energy of the (CO(2))(-) intermediate, most likely by complexation, and thereby lower the initial reduction barrier. The silver cathode then catalyzes formation of the final products. Formation of gaseous CO is first observed at an applied voltage of 1.5 volts, just slightly above the minimum (i.e., equilibrium) voltage of 1.33 volts. The system continued producing CO for at least 7 hours at Faradaic efficiencies greater than 96%.     

Organic superconductors--new benchmarks

Recent advances in the design and synthesis of organic synthetic metals have yielded materials that have the highest superconducting transition temperatures (T(c) approximately 13 kelvin) reported for these systems. These materials have crystal structures consisting of alternating layers of organic donor molecules and inorganic anions. Organic superconductors have various electronic and magnetic properties and crystal structures that are similar to those of the inorganic copper oxide superconductors (which have high T(c) values); these similarities include highly anisotropic conductivities, critical fields, and short coherence lengths. The largest number of organic superconductors, including those with the highest T(c) values, are charge-transfer salts derived from the electron donor molecule BEDT-TTF or ET [bis(ethylenedithio)-tetrathiafulvalene]. The synthesis and crystal structures of these salts are discussed; their electrical, magnetic, and band electronic structure properties and their many similarities to the copper oxide superconductors are treated as well.     

Room-Temperature, Electric Field-Induced Creation of Stable Devices in CulnSe2 Crystals

Multiple-junction structures were formed, on a microscopic scale, at room temperature, by the application of a strong electric field across originally homogeneous crystals of the ternary chalcopyrite semiconductor CulnSe(2). After removal of the electric field, the structures were examined with electron beam-induced current microscopy and their current-voltage characteristics were measured. Bipolar transistor action was observed, indicating that sharp bulk junctions can form in this way at low ambient temperatures. The devices are stable under normal (low-voltage) operating conditions. Possible causes for this effect, including electromigration and electric field-assisted defect reactions, are suggested.     

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.     

Experimental constraints on the theory of high-tc superconductivity

Analysis of the many experiments on high-temperature superconductivity indicate several essential aspects of any theory. The conductivity and other transport properties as a function of disorder, temperature, and frequency point to a non-Fermi liquid-like behavior, whereas photoemission experiments and magnetic properties indicate the presence of a Fermi surface in momentum space. To reconcile this apparent contradiction, a new type of electron liquid, called a Luttinger liquid, has been postulated, and the present article aims to show the need for this postulate. Theory and experiment indicate that the suitable phenomenological electronic structure model of the CuO layers is that of the one-band Hubbard model. It is also argued that experiment clearly indicates that interlayer interactions strongly affect the superconducting transition temperature, T(c), consistent with the fact that no theoretical calculations on two-dimensional Hubbard models have resulted in the prediction of high transition temperatures, and that anyon models are not favored by experiment.     

A Fluorite Isotype of SnO2 and a New Modification of TiO2: Implications for the Earth's Lower Mantle

The existence of a cubic fluorite-type SnO(2) and a hexagonal TiO(2) (which may be related to the fluorite structure) have been demonstrated by an in situ x-ray diffraction study in which a diamond-anvil pressure cell was used after the samples had been heated by a continuous yttrium-aluminum-garnet laser. At room temperature, the lattice parameter for SnO(2) (fluorite) is a = 4.925 +/- 0.005 angstroms and those for TiO(2) (fluorite-related) are a = 9.22 +/- 0.01 angstroms and c = 5.685 +/- 0.006 angstroms at about 250 kilobars. The volume change associated with the transition from rutile to fluorite (or related structure) is about -8 percent for SnO(2) and -10.5 percent for TiO(2) at transition. Upon release of pressure, both the fluorite-type SnO(2) and the TiO(2) reverted to the alpha-PbO(2) structure at room temperature. The hypothesis that the earth's lower mantle is composed of oxide phases might be feasible if it were possible for SiO(2) to possess the fluorite structure or its related forms at high pressure, as shown for SnO(2) and TiO(2) in this study. The oxide hypothesis proposed here differs from that postulated by Birch in that the primary coordination of silicon is 6 for Birch's hypothesis and 8 for the hypothesis presented here.     

Solvated electrons in high-temperature melts and glasses of the room-temperature stable electride [Ca₂₄Al₂₈O₆₄]⁴⁺·4e⁻

Solvated electrons in alkali metal-ammonia solutions have attracted attention as a prototype electronic conductor and chemical reducing agent for over a century. However, solvated electrons have not been realized in a high-temperature melt or glass of an oxide system to date. We demonstrated the formation of persistent solvated electrons in both a high-temperature melt and its glass by using the thermally stable electride [Ca(24)Al(28)O(64)](4+)·4e(-) (C12A7:e(-)) and controlling the partial pressure of oxygen. The electrical and structural properties of the resulting melt and glass differ from those of the conventional C12A7:O(2-) oxide, exhibiting metallic and hopping conduction, respectively, and a glass transition temperature that is ~160 kelvin lower than that of C12A7:O(2-) glass. Solvated electrons reside in cage structures in C12A7:e(-) and form a diamagnetic paired state.     

外源NO对低温胁迫下黄瓜幼苗生长、叶片膜脂过氧化和光合作用的影响

以‘津春4号’黄瓜为试材,研究了外源NO对低温胁迫下黄瓜幼苗生长、膜脂过氧化和光合作用的影响。结果表明,在9℃/9℃(昼/夜)的低温胁迫下,黄瓜幼苗的生长受到严重抑制,干重、鲜重、叶绿素含量和光合速率显著下降,膜透性和MDA含量显著增加;而叶面喷施外源100 μmol·L-1 NO供体硝普钠(SNP) 显著缓解了低温对黄瓜幼苗的抑制作用,膜透性和MDA含量显著降低,叶绿素含量和光合速率显著升高。正常生长下叶面喷施NO对黄瓜幼苗无显著影响。     

Magnetic flux-line lattices and vortices in the copper oxide superconductors

A variety of recent experiments on both the static and the dynamic properties of vortices and flux-line lattices in the mixed state of the copper oxide superconductors are discussed. The experiments are of two basic types: (i) experiments that image the magnetic flux patterns either with magnetic decoration or neutrons and give information about static structures, and (ii) experiments that explore the dynamics of vortices either through the resistivity or other electrodynamic responses of the material. Results of these experiments argue in favor of the existence of a true phase transition in the high-field vortex state from a low-temperature superconducting vortex glass phase into a disordered high-temperature vortex fluid phase. The vortex glass phase transition model does a good job of explaining high-precision measurements of the dynamics at the transition. At low fields and temperatures, very long range hexatic order in the flux-line lattice is observed.     

灌浆结实期高温对杂交稻两优培九籽粒形成生理的影响

探讨灌浆结实期高温对杂交稻两优培九籽粒形成生理的影响.利用人工气候室在灌浆结实期进行高温(昼/夜温度为36.5℃/27.5℃)和适温(昼/夜温度为29.5℃/23.5℃)处理,对两优培九灌浆结实期籽粒质量、籽粒中直链淀粉和蛋白质质量分数及ADPG焦磷酸化酶(ADPGPase)、颗粒结合型淀粉合成酶(GB-SS)、谷草转氨酶(GOT)和谷丙转氨酶(GPT)活性进行分析.结果表明,在高温条件下,籽粒直链淀粉积累快,粒质量增长快,成熟后籽粒质量和直链淀粉质量分数较适温条件下低,而蛋白质质量分数较适温条件下高.在高温条件下,籽粒中ADPGPase和GBSS活性在始花后前10d活性较适温条件下高,始花10d后迅速下降；GOT和GPT活性先升后降,均在始花后10 d出现峰值.在适温条件下,籽粒中ADPGPase和GBSS活性在始花后13d达到其活性高峰值,GOT和GPT活性均呈缓慢下降趋势,但始花13d后ADPGPase、GBSS、GOT和GPT活性均不同程度地高于高温处理.可见,在灌浆中后期,相对低的日均温度有助于提高两优培九籽粒中ADPGPase、GBSS、GOT和GPT活性和改善稻米品质.     

Understanding reactivity at very low temperatures: the reactions of oxygen atoms with alkenes

A remarkable number of reactions between neutral free radicals and neutral molecules have been shown to remain rapid down to temperatures as low as 20 kelvin. The rate coefficients generally increase as the temperature is lowered. We examined the reasons for this temperature dependence through a combined experimental and theoretical study of the reactions of O(3P) atoms with a range of alkenes. The factors that control the rate coefficients were shown to be rather subtle, but excellent agreement was obtained between the experimental results and microcanonical transition state theory calculations based on ab initio representations of the potential energy surfaces describing the interaction between the reactants.     

Catalysis by transition metals: metal-carbon double and triple bonds

Several well-characterized transition metal catalysts contain a metal-carbon double bond or a metal-carbon triple bond. In other homogeneous (or heterogeneous) catalyst systems in which the metal is likely to be in a relatively high oxidation state, such as molybdenum(VI) or tungsten(VI), metal-carbon multiple bonds may play an important role. Some recent results suggest that even supposedly well understood reactions such as ethylene polymerization may actually involve catalysts that behave as if they contained a metal-carbon double bond instead of a metal-carbon single bond. The chemistry of metal-carbon double and triple bonds should eventually complement and perhaps. overlap the known chemistry of complexes containing metal-oxygen double bonds or metal-nitrogen triple bonds, respectively; unique catalytic reactions involving carbon, nitrogen, and oxygen ligands multiply bonded to transition metals are therefore possible.     

High-Tc Molecular-Based Magnets: Ferrimagnetic Mixed-Valence Chromium(III)-Chromium(II) Cyanides with Tc at 240 and 190 Kelvin

Molecular-based magnets with high magnetic-ordering temperatures, T(c), can be obtained by mild chemistry methods by focusing on the bimetallic and mixed-valence transition metal micro-cyanide of the Prussian blue family. A simple orbital model was used to predict the electronic structure of the metal ions required to achieve a high ordering temperature. The synthesis and magnetic properties of two compounds, [Cr(5)(CN)(12)].10H(2)O and Cs(0.75) [Cr(2.125)(CN)(6)].5H(2)O, which exhibited magnetic-ordering temperatures of 240 and 190 kelvin, respectively, are reported, together with the strategy for further work.     

Seawater chemistry and early carbonate biomineralization

The first appearances of aragonite and calcite skeletons in 18 animal clades that independently evolved mineralization during the late Ediacaran through the Ordovician (approximately 550 to 444 million years ago) correspond to intervals when seawater chemistry favored aragonite and calcite precipitation, respectively. Skeletal mineralogies rarely changed once skeletons evolved, despite subsequent changes in seawater chemistry. Thus, the selection of carbonate skeletal minerals appears to have been dictated by seawater chemistry at the time a clade first acquired its mineralized skeleton.     

A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles

The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an e(g) symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds.     

Synthesis of Isocyanic Acid from Nitric Oxide over Palladium and Iridium Catalysts

A novel and convenient synthesis of isocyanic acid (HNCO) and its trimer isocyanuric acid has been obtained by the conversion of nitric oxide (NO). Nitric oxide, carbon monoxide, and hydrogen mixed in helium at the level of 0.3 to 5 percent reacted over iridium and palladium catalysts at 280 degrees to 450 degrees C to form HNCO in 60 to 75 percent yield. Major side products were ammonium cyanate at low temperature and ammonia or nitrogen at high temperature. Total conversion of nitrogen from NO to NCO reached 73 percent over palladium and 86 percent over iridium.     

黄瓜幼苗干旱-低温交叉适应与渗透调节的关系

 【目的】探讨干旱诱导黄瓜幼苗对低温胁迫的交叉适应机理。【方法】以‘津优3号’幼苗为试材,用10 %聚乙二醇(PEG-6000)溶液模拟干旱预处理黄瓜幼苗2 d,未经预处理的作对照。恢复2 d后在光照培养箱中进行低温(昼/夜温度8℃/5℃)处理。【结果】低温胁迫可使黄瓜幼苗叶片的相对含水量、水势和渗透势显著降低,可溶性糖、脯氨酸和可溶性蛋白的含量明显增加。胁迫前经PEG预处理,黄瓜幼苗叶片的相对含水量、水势和渗透势的降低幅度明显减小,脯氨酸、可溶性糖和可溶性蛋白质含量则显著增加。低温胁迫结束时(7 d)时,PEG处理黄瓜幼苗叶片的相对含水量比对照高24.7个百分点,水势和渗透势分别比对照高0.35 MPa和0.13 MPa;脯氨酸、可溶性糖和可溶性蛋白质含量分别比对照高41.4 %、80.8 %和260.7 %。【结论】干旱预处理可诱导黄瓜幼苗对低温胁迫的交叉适应性,这种适应性与渗透调节能力的增强有关。     

Reaction of plutonium dioxide with water: formation and properties of PuO(2+x)

Results show that PuO(2+x), a high-composition (x 相似文献