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.     

Ordering of V2+, Mn2+, and Fe3+ Ions in Zoisite, Ca2Al3Si3O12(OH)

The presence of very small amounts of Mn(2+), V(2+), and Fe(3+) ions in zoisite can be easily detected by the electron paramagnetic resonance technique at room temperature. The Mn(2+) and Fe(3+) ions are completely ordered and are probably located in the Ca(1)- and Al(II)-sites, respectively, whereas the V(2+) ions probably occupy both Ca(1)- and Ca(2)-sites, with a preference for the Ca(1)-site.     

Fresnoite: unusal titanium coordination

The crystal structure of fresnoite, Ba(2)(TiO)[Si(2)O(7)], consists of [Si(2)O(7)](6-) double groups and titanium-centered square pyramids linked to form flat sheets. Intercalated between these sheets are Ba(2+) ions in highly distorted pentagonal antiprisms. The structure of fresnoite is related to that of melilite, (Ca,Na)(2)(Mg,Al[Si(2)(7)].     

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。     

A New High-Temperature Superconductor: Bi2Sr3-x Cax Cu2O8+y

A new superconductor that displays onset behavior near 120 K has been identified as Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y), with x ranging from about 0.4 to 0.9. Single crystal x-ray diffraction data were used to determine a pseudo-tetragonal structure based on an A-centered orthorhombic subcell with a = 5.399 A, b= 5.414A, and c = 30.904 A. The structure contains copper-oxygen sheets as in La(2)CuO(4) and YBa(2)Cu(3)O(7), but the copper-oxygen chains present in YBa(2)Cu(3)O(7) do not occur in Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y). The structure is made up of alternating double copper-oxygen sheets and double bismuth-oxygen sheets. There are Ca(2+) and Sr(2+) cations between the adjacent Cu-O sheets; Sr(2+) cations are also found between the Cu-O and Bi-O sheets. Electron microscopy studies show an incommensurate superstructure along the a axis that can be approximated by an increase of a factor of 5 over the subcell dimension. This superstructure is also observed by x-ray diffraction on single crystals, but twinning can make it appear that the superstructure is along both a and b axes. Flux exclusion begins in our samples at about 116 K and is very strong by 95 K. Electrical measurements on a single crystal of Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y) show a resistivity drop at about 116 K and apparent zero resistivity at 91 K.     

Magnetic resonance properties of some lunar material

Paramagnetic resonance spectra of Apollo 11 fines and rocks were measured at 9 and 35 gigahertz and at 4 degrees , 80 degrees , and 300 degrees K. At both frequencies the material has an intense absorption at g = 2, with a line width of approximately 950 gauss. Fe ions with strong exchange interactions produce this resonance. A comparison of the resonance absorption due to Fe(3+) showed that the energy of the crystal field interaction was approximately 0.1 per centimeter. Mn(2+) was identified in several samples, and an absorption at g = 1.89 was tentatively attributed to Ti(3+). The nuclear magnetic resonance spectra of (27)Al had a distribution of asymmetry parameters eta ranging from 0.25 to 0.75 and had nuclear quadrupole coupling constants e(2)qQ/h of approximately 3 megahertz.     

Polymorphs of Alumina Predicted by First Principles: Putting Pressure on the Ruby Pressure Scale

Fully optimized quantum mechanical calculations indicate that Al2O3 transforms from the corundum structure to the as yet unobserved Rh2O3 (II) structure at about 78 gigapascals, and it further transforms to Pbnm-perovskite structure at 223 gigapascals. The predicted x-ray spectrum of the Rh2O3 (II) structure is similar to that of the corundum structure, suggesting that the Rh2O3 (II) structure could go undetected in high-pressure x-ray measurements. It is therefore possible that the ruby (Cr3+-doped corundum) fluorescence pressure scale is sensitive to the thermal history of the ruby chips in a given experiment.     

Eclogitic pyroxenes, ordered with p2 symmetry

X-ray diffraction crystal-structure analysis of omphacite from eclogite, Tiburon Peninsula, Marin County, California, shows that this clinopyroxene has P2 symmetry with a nearly ordered distribution of the multiple cation content defined by its approximate formula: (Na(o.5) Ca(o.5)) (Mg(o.4)Fe(2)+( 0.1) Al(0.4) Fe(3) +(0.1)) Si(2)0(6). Na+ and Ca(2+) tend to assume alternate locations in the structure, and ( Mg,Fe(2+)) octahedra alternate with Al(3+). or (Al,F(3+)) octahedra in chains along c.     

土壤铝存在形式对马铃薯抵抗侵染软腐病菌的影响

[目的]从土壤化学角度探讨西北地区适合种植马铃薯的病理原因。[方法]通过模拟酸性及碱性土壤中铝的2种形式氯化铝(Al3+)和胶体铝(Al(OH)3),研究马铃薯块茎受软腐病菌侵染时土壤胶体态的铝对块茎过氧化氢积累及病程蛋白表达的影响。[结果]土壤铝的溶出直接导致马铃薯块茎切片细胞的死亡。马铃薯感染软腐病菌过程中,Al3+处理加速了马铃薯的感病,而Al(OH)3则延缓了马铃薯的感病。Al3+处理在加速马铃薯细胞死亡的同时产生大量的H2O2,而Al(OH)3在产生较高H2O2积累的同时并未造成明显的马铃薯细胞死亡。SDS-PAGE电泳分析表明,Al(OH)3处理的马铃薯明显不同于Al3+及空白对照。[结论]马铃薯块茎在感病过程中受土壤铝溶出率及铝形态变化的双重影响。     

First occurrence of the garnet-ilmenite transition in silicates

Pyrope garnet (Mg(3)Al(2)Si(3)O(12)) has been found to transform to an ilmenite-type phase at a loading pressure between 240 and 250 kilobars and at about 1000 degrees to 1400 degrees C in a diamond-anvil press coupled with laser heating. The lattice parameters for the ilmenite-type phase of (Mg(.75) Al(.25))(Si(.75) Al(.25))O(3) are a(0) = 4.755 +/- 0.002 and c(0) = 13.360 +/- 0.005 angstroms. The zero-pressure volume change associated with the garnet-ilmenite transition is calculated to be -7.1 percent. This result verifies the prediction that pyrope garnet would transform to the ilmenite structure at high pressure first suggested in 1962 by Clark et al. and Ringwood.     

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。     

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.     

高温热化法制备磷脂酰胆碱方法研究

[目的]用高温热化法来制备磷脂酰胆碱。[方法]将磷脂原料高温加热,使所有非胆碱磷脂降解,然后用丙酮处理磷脂原料热化物,沉淀出包含磷脂酰胆碱在内的丙酮不溶物(AI),接着用乙醇处理AI,离心分离,得墨黑色乙醇可溶物(ES)溶液,最后对ES溶液进行脱色,得磷脂酰胆碱产品,采用氧化铝层层析、活性炭多次吸附、氧化铝二次吸附、活性炭吸附结合氧化铝吸附几种方法对ES溶液进行脱色,并进行比较研究。[结果]结果表明:这几种脱色方法对产品的品质都有不同程度的改善,不同的脱色方法所得产品的PC有很大差别。[结论]氧化铝层层析法对ES溶液脱色效果最好,其产品的PC含量可达90%以上。     

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.     

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.     

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.     

Color center in amethyst quartz

Treatment with x-rays increased the intensity of color of natural amethyst up to fivefold, and an electron paramagnetic resonance spectrum was detected. The intensity of the spectrum was proportional to the intensity of the optical absorption near 545 mmicro. The EPR spectrum of the color center corresponded to a positive hole trapped on a substitutional Fe(3+) ion in the quartz structure. We ascribe the color to a charge-transfer transition, Fe(4+) + O(2)- --> Fe(3+) + O(1-).     

Coking- and sintering-resistant palladium catalysts achieved through atomic layer deposition

We showed that alumina (Al(2)O(3)) overcoating of supported metal nanoparticles (NPs) effectively reduced deactivation by coking and sintering in high-temperature applications of heterogeneous catalysts. We overcoated palladium NPs with 45 layers of alumina through an atomic layer deposition (ALD) process that alternated exposures of the catalysts to trimethylaluminum and water at 200°C. When these catalysts were used for 1 hour in oxidative dehydrogenation of ethane to ethylene at 650°C, they were found by thermogravimetric analysis to contain less than 6% of the coke formed on the uncoated catalysts. Scanning transmission electron microscopy showed no visible morphology changes after reaction at 675°C for 28 hours. The yield of ethylene was improved on all ALD Al(2)O(3) overcoated Pd catalysts.     

棕色尖晶石颜料的合成

介绍了如下几种色料的制备：(1)ZnFeCrO4；(2)ZnFeCrO4中部份ZnO被FeO或NiO FeO所置换；(3)ZnFeCrO4中部份Fe2O3或部份Fe2O3 Cr2O3被Al2O3所置换。借助热分析和X—射线衍射分析讨论了色料的合成过程和晶体结构。最后，通过色釉试验，参照色度测定数据，阐述了颜料的组成和结构对色釉颜色的影响。表明铁离子出现在尖晶石结构中四面体间隙位和八面体间隙位的能力是极为重要的。如果Fe^3 尽量少地占据四面体间隙位，则出现制出红色值对黄色值之比趋向极大的红棕色。     

A solid sulfur cathode for aqueous batteries

Because of its high resistivity and subsequent low electroactivity, sulfur is not normally considered a room-temperature battery cathode. An elemental sulfur cathode has been made with a measured capacity of over 900 ampere.hours per kilogram, more than 90 percent of the theoretical storage capacity of solid sulfur at room temperature, accessed by means of a lightweight, highly conductive, aqueous polysulfide interface through the electrocatalyzed reaction S + H(2)O + 2e(-) --> HS(-) + OH(-). This solid sulfur cathode was first used in a battery with an aluminum anode for an overall discharge reaction 2Al + 3S + 3OH(-) + 3H(2)O --> 2Al(OH)(3) + 3HS(-), giving a cell potential of 1.3 volts. The theoretical specific energy of the aluminum-sulfur battery (based on potassium salts) is 910 watt.hours per kilogram with an experimental specific energy of up to 220 watt.hours per kilogram.