The hydride anion in an extended transition metal oxide array: LaSrCoO3H0.7

We present the synthesis and structural characterization of a transition metal oxide hydride, LaSrCoO3H0.7, which adopts an unprecedented structure in which oxide chains are bridged by hydride anions to form a two-dimensional extended network. The metal centers are strongly coupled by their bonding with both oxide and hydride ligands to produce magnetic ordering at temperatures up to at least 350 kelvin. The synthetic route is sufficiently general to allow the prediction of a new class of transition metal--containing electronic and magnetic materials.     

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.     

Stable low-pressure hydrogen clusters stored in a binary clathrate hydrate

Thermodynamic, x-ray diffraction, and Raman and nuclear magnetic resonance spectroscopy measurements show that clusters of H2 can be stabilized and stored at low pressures in a sII binary clathrate hydrate. Clusters of H2 molecules occupy small water cages, whereas large water cages are singly occupied by tetrahydrofuran. The presence of this second guest component stabilizes the clathrate at pressures of 5 megapascals at 279.6 kelvin, versus 300 megapascals at 280 kelvin for pure H2 hydrate.     

Unexpected stability of Al4H6: a borane analog?

Whereas boron has many hydrides, aluminum has been thought to exhibit relatively few. A combined anion photoelectron and density functional theory computational study of the Al4H-6 anion and its corresponding neutral, Al4H6, showed that Al4H6 can be understood in terms of the Wade-Mingos rules for electron counting, suggesting that it may be a borane analog. The data support an Al4H6 structure with a distorted tetrahedral aluminum atom framework, four terminal Al-H bonds, and two sets of counter-positioned Al-H-Al bridging bonds. The large gap between the highest occupied and the lowest unoccupied molecular orbitals found for Al4H6, together with its exceptionally high heat of combustion, further suggests that Al4H6 may be an important energetic material if it can be prepared in bulk.     

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.     

Metastable phases in polar stratospheric aerosols

Phase changes in stratospheric aerosols were studied by cooling a droplet of sulfuric acid (H(2)SO(4)) in the presence of nitric acid (HNO(3)) and water vapor. A sequence of solid phases was observed to form that followed Ostwald's rule for phase nucleation. For stratospheric partial pressures at temperatures between 193 and 195 kelvin, a metastable ternary H(2)SO(4)-HNO(3) hydrate, H(2)SO(4) . HNO(3) . 5H(2)O, formed in coexistence with binary H(2)SO(4) . kH(2)O hydrates (k = 2, 3, and 4) and then transformed to nitric acid dihydrate, HNO(3) . 2H(2)O, within a few hours. Metastable HNO(3) . 2H(2)O always formed before stable nitric acid trihydrate, HNO(3).3H(2)O, under stratospheric conditions and persisted for long periods. The formation of metastable phases provides a mechanism for differential particle growth and sedimentation of HNO(3) from the polar winter stratosphere.     

Growth of SiO2 at room temperature with the use of catalyzed sequential half-reactions

Films of silicon dioxide (SiO2) were deposited at room temperature by means of catalyzed binary reaction sequence chemistry. The binary reaction SiCl4 + 2H2O --> SiO2 + 4HCl was separated into SiCl4 and H2O half-reactions, and the half-reactions were then performed in an ABAB ellipsis sequence and catalyzed with pyridine. The pyridine catalyst lowered the deposition temperature from >600 to 300 kelvin and reduced the reactant flux required for complete reactions from approximately 10(9) to approximately 10(4) Langmuirs. Growth rates of approximately 2.1 angstroms per AB reaction cycle were obtained at room temperature for reactant pressures of 15 millitorr and 60-second exposure times with 200 millitorr of pyridine. This catalytic technique may be general and should facilitate the chemical vapor deposition of other oxide and nitride materials.     

Evidence for Superfluidity in Para-Hydrogen Clusters Inside Helium-4 Droplets at 0.15 Kelvin

A linear carbonyl sulfide (OCS) molecule surrounded by 14 to 16 para-hydrogen (pH(2)) molecules, or similar numbers of ortho-deuterium (oD(2)) molecules, within large helium-4 ((4)He) droplets and inside mixed (4)He/(3)He droplets was investigated by infrared spectroscopy. In the pure (4)He droplets (0.38 kelvin), both systems exhibited spectral features that indicate the excitation of angular momentum around the OCS axis. In the colder (4)He/(3)He droplets (0.15 kelvin), these features remained in the oD(2) cluster spectra but disappeared in the pH(2) spectra, indicating that the angular momentum is no longer excited. These results are consistent with the onset of superfluidity, thereby providing the first evidence for superfluidity in a liquid other than helium.     

Antiferromagnetic Ordering and Paramagnetic Behavior of Ferromagnetic Cu6 and Cu18 Clusters in BaCuO2+x

Magnetization and neutron diffraction measurements on polycrystalline BaCuO2+x revealed a combination of magnetic behaviors. The Cu(6) ring clusters and Cu(18) sphere clusters in this compound had ferromagnetic ground states with large spins 3 and 9, respectively. The Cu(6) rings ordered antiferromagnetically below the Néel temperature T(N) = 15 +/- 0.5 kelvin, whereas the Cu(18) spheres remained paramagnetic down to 2 kelvin. The ordered moment below T(N) was 0.89(5) Bohr magnetons per Cu in the Cu(6) rings, demonstrating that quantum fluctuation effects are small in these atomic clusters. The Cu(18) clusters are predicted to exhibit ferromagnetic intercluster order below about 1 kelvin.     

Mg/Al ordering in layered double hydroxides revealed by multinuclear NMR spectroscopy

The anion-exchange ability of layered double hydroxides (LDHs) has been exploited to create materials for use in catalysis, drug delivery, and environmental remediation. The specific cation arrangements in the hydroxide layers of hydrotalcite-like LDHs, of general formula Mg2+(1-x)Al3+(x)OH2(Anion(n-)(x/n)).yH2O, have, however, remained elusive, and their elucidation could enhance the functional optimization of these materials. We applied rapid (60 kilohertz) magic angle spinning (MAS) to obtain high-resolution hydrogen-1 nuclear magnetic resonance (1H NMR) spectra and characterize the magnesium and aluminum distribution. These data, in combination with 1H-27Al double-resonance and 25Mg triple-quantum MAS NMR data, show that the cations are fully ordered for magnesium:aluminum ratios of 2:1 and that at lower aluminum content, a nonrandom distribution of cations persists, with no Al3+-Al3+ close contacts. The application of rapid MAS NMR methods to investigate proton distributions in a wide range of materials is readily envisaged.     

Rapid formation of sulfuric acid particles at near-atmospheric conditions

We investigated the formation of new particles in a laboratory study, starting from H2SO4 produced in situ through the reaction of OH radicals with SO2. Newly formed particles were observed for H2SO4 concentrations above 7 x 10(6) per cubic centimeter. At 293 kelvin, a rough estimate yielded a nucleation rate of 0.3 to 0.4 particles per cubic centimeter per second for approximately 10(7) particles per cubic centimeter of H2SO4 (particle size >/= 3 nanometers). These findings are in agreement with observations from the atmosphere. The results demonstrate that under laboratory conditions similar to the atmosphere, particle formation occurs at atmospheric H2SO4 concentration levels.     

Pressure Dependence of Superconductivity in Single-Phase K3C60

The superconducting compound K(3)C(60) (with transition temperature T(c) = 19.3 kelvin at ambient pressure), formed as a single phase by reaction of alkali vapor with solids of the icosahedral C(60) molecule (buckminsterfullerene), shows a very large decrease of T(c) with increasing pressure. Susceptibility measurements on sintered pellets showing bulk superconductivity are reported up to 21 kilobars of pressure, where T(c) is already less than 8 kelvin. The results are consistent with a piling up of the density of states at the Fermi level.     

The structure of the c60 molecule: x-ray crystal structure determination of a twin at 110 k

Single-crystal x-ray diffraction methods were used to determine the crystal and molecular structure of C(60) buckminsterfullerene. At 110 kelvin C(60) is cubic, apparent Laue symmetry m3m, but it exhibits noncrystallographic systematic extinctions indicative of a twin in which I(hkl) and I(khl) are superimposed. In fact, C(60) crystallizes with four molecules in space group [See equation in the PDF file] of the cubic system (Laue symmetry m3) with lattice constant a = 14.052(5) angstroms (A) at 110 kelvin. The twin components are equal. A given component, which has crystallographically imposed symmetry [See equation in the PDF file] displays an ordered structure of a truncated icosahedron. The five independent C=C bonds that join C(6) rings average 1.355(9) A; the ten independent C-C bonds that join C(6) and C(5) rings average 1.467(21) A. The mean atom-to-atom diameter of the C(60) molecule is 7.065(3) A. The molecules are very tightly packed in the crystal structure, with intermolecular C...C distances as short as 3.131(7) A.     

The origin of aluminum flocs in polluted streams

About 240,000 square kilometers of Earth's surface is disrupted by mining, which creates watersheds that are polluted by acidity, aluminum, and heavy metals. Mixing of acidic effluent from old mines and acidic soils into waters with a higher pH causes precipitation of amorphous aluminum oxyhydroxide flocs that move in streams as suspended solids and transport adsorbed contaminants. On the basis of samples from nine streams, we show that these flocs probably form from aggregation of the epsilon -Keggin polyoxocation AlO4Al12(OH)24(H2O)12(7+)(aq) (Al13), because all of the flocs contain distinct Al(O)4 centers similar to that of the Al13 nanocluster.     

Low-temperature synthesis of zintl compounds with a single-source molecular precursor

Thermolysis of the heterobimetallic phosphinidene complex [Sb(PCy)3]2- Li6.6HNMe2 (Cy = C6H11) at 303 to 313 kelvin gives Zintl compounds containing (Sb7)3- anions. The complex thus constitutes a stable molecular single-source precursor to Zintl compounds and provides a potential low-temperature route to photoactive alkali metal antimonates. The new chemical reaction involved, which is driven thermodynamically by the formation of P-P bonds, has implications in the low-temperature synthesis of other technologically important materials (such as gallium arsenide).     

生物炭对铝富集酸性土壤的毒性缓解效应及潜在机制

【目的】红壤铝毒是土壤改良持续关注的问题之一。生物炭因其自身的理化和生物学特性,为探索解决该难题提供了新的思路和途径。论文通过在红壤中添加外源铝并种植作物,研究生物炭对铝富集土壤铝毒的缓解效应及潜在机制。【方法】选用酸性红壤做盆栽试验,种植小白菜,添加花生壳生物炭和外源铝,设置CK(0C+0Al)、C(2%C)、Al(1 mmol·L~(~(-1))Al)、C+Al(2%C+1 mmol·L~(~(-1))Al)4个处理,分析生物炭对铝富集红壤不同活性铝及作物生长的影响。【结果】铝毒会显著抑制小白菜的出苗,且加重红壤小白菜生长受抑制的情况,降低小白菜的生物量,同时,铝毒会显著提高小白菜铝含量。而施用生物炭能缓解铝毒对小白菜的抑制影响,显著改善小白菜的生长状况,降低小白菜铝含量,C+Al处理小白菜铝含量较Al处理降低89.4%。铝毒会显著降低红壤的pH,Al处理红壤pH较CK处理降低了0.36个单位,而施用生物炭能显著提高土壤pH,C+Al处理土壤pH较Al处理上升0.62个单位。Al处理较CK处理土壤活性铝含量上升276.4μg·g~(-1),远大于添加量(27μg·g~(-1)),而施用生物炭能显著降低土壤活性铝含量,C+Al处理较Al处理下降14.9%。此外,Al处理交换性Al~(3+)含量较CK处理上升23.1%,施用生物炭后,C+Al处理交换性Al~(3+)含量较Al处理下降46.5%。CK与Al处理土壤活性铝形态主要以具有生物毒害性的交换性Al~(3+)为主,C与C+Al处理土壤活性铝形态主要以单聚体羟基铝离子、胶体Al(OH)30为主。【结论】添加外源铝降低了土壤pH,加重铝的毒害,抑制作物的生长发育。此外,外源铝的添加对红壤中活性铝有较强的激发效应,使得交换性Al~(3+)含量显著升高。然而,生物炭能显著提高酸性土壤pH,且改变不同活性铝的含量,但其对4种不同形态活性铝的效应有较大差异,其主要通过降低具有生物毒性的Al~(3+)含量来缓解铝毒,从而改善作物生长状况。     

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.     

Photoinduced Magnetization of a Cobalt-Iron Cyanide

Photoinduced magnetization was observed in a Prussian blue analog, K0.2Co1.4- [Fe(CN)6]·6.9H2O. An increase in the critical temperature from 16 to 19 kelvin was observed as a result of red light illumination. Moreover, the magnetization in the ferrimagnetic region below 16 kelvin was substantially increased after illumination and could be restored almost to its original level by thermal treatment. These effects are thought to be caused by an internal photochemical redox reaction. Furthermore, blue light illumination could be used to partly remove the enhancement of the magnetization. Such control over magnetic properties by optical stimuli may have application in magneto-optical devices.     

Proximity-induced superconductivity in DNA

Conductivity measurements on double-stranded DNA molecules deposited by a combing process across a submicron slit between rhenium/carbon metallic contacts reveal conduction to be ohmic between room temperature and 1 kelvin. The resistance per molecule is less than 100 kilohm and varies weakly with temperature. Below the superconducting transition temperature (1 kelvin) of the contacts, proximity-induced superconductivity is observed. These results imply that DNA molecules can be conducting down to millikelvin temperature and that phase coherence is maintained over several hundred nanometers.     

Melting of H2SO4·4H2O Particles upon Cooling: Implications for Polar Stratospheric Clouds

Polar stratospheric clouds (PSCs) are important for the chemical activation of chlorine compounds and subsequent ozone depletion. Solid PSCs can form on sulfuric acid tetrahydrate (SAT) (H2SO4·4H2O) nuclei, but recent laboratory experiments have shown that PSC nucleation on SAT is strongly hindered. A PSC formation mechanism is proposed in which SAT particles melt upon cooling in the presence of HNO3 to form liquid HNO3-H2SO4-H2O droplets 2 to 3 kelvin above the ice frost point. This mechanism offers a PSC formation temperature that is defined by the ambient conditions and sets a temperature limit below which PSCs should form.