Synthesis of Dimethyl Carbonate from CO2 , Methanol, and Epoxides Using Re（CO） 5 Cl/K2 CO3 as Catalyst System

IntroductionOver the past few years, dimethyl carbonate(DMC) has been proven to be an efficientmethylating,methoxylating, and methoxycarbonylating agent inorganic syntheses, in which DMC is used to replace thetoxic methyl halides, dimethyl sulfate or carb     

Inhibition of the reduction of Cr(VI) at the magnetite–water interface by calcium carbonate coatings

The effect of calcium carbonate coatings on the reduction of aqueous chromate on the magnetite(1 1 1) surface has been investigated using a combination of synchrotron based X-ray photoemission spectroscopy (PES) and X-ray absorption near edge structure (XANES) spectroscopy, along with laboratory-based powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). CaCO₃ coatings (dominantly calcite with minor quantities of aragonite and vaterite) of thicknesses ranging from 10 Å to 20 m were grown on magnetite(1 1 1) surfaces by exposure to supersaturated aqueous solutions followed by evaporation of the solution—a process that mimics pore-water evaporation in vadose zones leading to the formation of caliche and calcium carbonate coatings on mineral grains. Coating thicknesses were determined from attenuation of the Fe 2p photoemission signal by the carbonate coating. For coatings less than 15 Å thick, Cr 2p photoemission and Cr L_II, L_III-edge XANES spectra show that chromate is reduced by the underlying magnetite surface; however, as the minimum coating thickness increases beyond 15 Å, the magnetite surface becomes passivated and further chromate reduction ceases. Our findings suggest that carbonate coatings on natural magnetite grains can significantly reduce or eliminate their ability to reduce Cr(VI), which is a toxic and highly mobile environmental contaminant.     

可降解自固化类骨磷灰石支架的研究

0引言一直以来,钙磷生物材料如羟基磷灰石(hy-droxyapatite,HA)由于其成份与骨的无机成份相似,具有良好的生物相容性,作为骨修复材料引起了人们广泛的兴趣。磷酸钙骨水泥是一类可在生理条件下自固化的非陶瓷型类HA人工骨材料,这种由磷酸钙骨水泥(calcium phosphate cement,CPC)转变而成的HA,与天然骨磷灰石有类似的组成结构,植入人体后可参与新陈代谢,促进骨组织生长[1,2]。一些研究显示,CPC具有成骨活性和生物降解性,在体内被吸收的同时可引导新骨的生成,从而可克服自体骨、磷酸三钙陶瓷因吸收降解过快造成的局部缺陷以及陶瓷型HA长…     

Nickel Aqueous Speciation and Solubility at Ambient Conditions: A Thermodynamic Elegy

Summary.  This review reveals that, in contrast to the general opinion, the aqueous speciation of nickel is poorly known. Besides the fairly well established first hydrolysis constant, data are scarce and only poor estimates can be derived for higher Ni hydrolysis constants from a few solubility studies. The situation is even worse in the case of aqueous carbonate complexes. No reliable experimental study has been published so far and almost all numbers reported in thermodynamic databases are unacceptable estimates. In this review we scrutinise all these published estimates and propose expectation ranges of nickel carbonate complex stability through correlation with other known thermodynamic constants. Solubility constants for a few simple nickel solids are known or have been estimated from thermochemical data. However, none of these simple solids is of geochemical relevance at ambient conditions. Based on field evidence, classes of solids are identified which potentially govern nickel concentrations in ground and surface waters. Recent spectroscopic data indicate that magnesium clay minerals and layered double hydroxides are the most prominent candidates for nickel-bearing solids at ambient conditions. Corresponding author. E-mail: wolfgang.hummel@psi.ch Dedicated to the memory of Prof. Rolf Grauer Received January 14, 2003; accepted January 24, 2003 Published online May 15, 2003     

Synthesis and Crystal Structure of MnSm_4(SiO_4)_3O

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Thermal transformations in phosphorites

The thermal transformations in phosphorites during flash calcination were investigated by FT-IR spectroscopy, X-ray diffraction and chemical analyses. During flash calcination changes occur, both in the composition of the phosphorite and in the crystallochemistry of the fluor-carbonate-apatite (francolite). The former changes include: decomposition of a great part of the calcite in the rock and oxidation of organic matter. The latter changes include: partial removal of the structural carbonate; partial relocation of the remaining carbonate ions in the apatite structure; a new arrangement of hydroxyl groups and fluorine on the hexagonal axis; partial condensation of the orthophosphate groups and increase of crystallite sizes. Isomorphous substitution of PO ₄ ^–3 in apatite by SO ₄ ^–2 and SiO ₄ ^–4 may take place.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthdayThe financial support from Rotem-Amfert-Negev Phosphate Co. is gratefully acknowledged. We thank Dr. B. Pregerson of the Rotem-Amfert-Negev for supplying samples     

Chromium(III) Hydroxide Solubility in the Aqueous K+-H+-OH?-CO2-HCO 3? -CO 32? -H2O System: A?Thermodynamic Model

Chromium(III)-carbonate reactions are expected to be important in managing high-level radioactive wastes. Extensive studies on the solubility of amorphous Cr(III) hydroxide solid in a wide range of pH (3–13) at two different fixed partial pressures of CO₂(g) (0.003 or 0.03 atm.), and as functions of K₂CO₃ concentrations (0.01 to 5.8 mol⋅kg⁻¹) in the presence of 0.01 mol⋅dm⁻³ KOH and KHCO₃ concentrations (0.001 to 0.826 mol⋅kg⁻¹) at room temperature (22±2 °C) were carried out to obtain reliable thermodynamic data for important Cr(III)-carbonate reactions. A combination of techniques (XRD, XANES, EXAFS, UV-Vis-NIR spectroscopy, thermodynamic analyses of solubility data, and quantum mechanical calculations) was used to characterize the solid and aqueous species. The Pitzer ion-interaction approach was used to interpret the solubility data. Only two aqueous species [Cr(OH)(CO₃)₂²⁻ and Cr(OH)₄CO₃³⁻] are required to explain Cr(III)-carbonate reactions in a wide range of pH, CO₂(g) partial pressures, and bicarbonate and carbonate concentrations. Calculations based on density functional theory support the existence of these species. The log ₁₀ K° values of reactions involving these species [{Cr(OH)₃(am) + 2CO₂(g)⇌Cr(OH)(CO₃)₂²⁻+2H⁺} and {Cr(OH)₃(am) + OH⁻+CO₃²⁻ ⇌Cr(OH)₄CO₃³⁻}] were found to be −(19.07±0.41) and −(4.19±0.19), respectively. No other data on any Cr(III)-carbonato complexes are available for comparisons.     

Gas diffusion-flow injection determination of total inorganic carbon in water using tungsten oxide electrode

A novel gas diffusion-flow injection method has been developed for the rapid and sensitive determination of total inorganic carbon (TIC) in water. The method is based on the diffusion of CO₂ across gas permeable membrane from a donor stream containing 0.1 M HCl to an acceptor stream of sodium acetate (10⁻⁵ mol l⁻¹ and pH 10). The CO₂ trapped in the acceptor stream passes through an electrochemical flow cell contains a tungsten oxide wire and a silver/silver chloride electrode, where it was sensitively detected. The parameters affecting the sensitivity of the electrode such as buffer concentration, pH, flow rate and injected volume were studied in detail. The electrode response was linear in the concentration range from 5 to 100 μg ml⁻¹ CO₃²⁻ with a correlation coefficient (R²) of 0.998. Precision (R.S.D.) was 1.42% for 20 μg ml⁻¹ standard solution of CO₃²⁻ (n=10). The detection limit was 0.20 μg ml⁻¹ CO₃²⁻. The method was evaluated by the injection of real natural water samples and an average recovery of 100.1% was obtained. The sampling rate was 30 samples h⁻¹. The method is simple, feasible with satisfactory accuracy and precision and thus could be used for monitoring TIC in water.     

Location of type B carbonate ion in type A-B carbonate apatite synthesized at high pressure

The structure of a complex, disordered type A-B carbonate apatite (CAp) of approximate composition Ca₁₀(PO₄)_6−y(CO₃)_x+(3/2)y(OH)_2−2x, x-0.7, y-0.6, synthesized at 3 GPa, 1400°C has been determined using single-crystal X-ray diffraction and FTIR spectroscopy at room temperature and pressure. Crystal data are: hexagonal, space group P6₃/m, Z=1; a=9.5143(3), c=6.8821(2) Å, V=539.5 Å³, and R=0.025. There are three structural locations for the carbonate ion. The channel carbonate is mainly in the closed vertical configuration of the structure, with two of its oxygen atoms close to the c-axis (A1 carbonate; IR bands at 1541 and 1449 cm⁻¹), but subordinate amounts are also located in an open vertical configuration (A2 carbonate; IR bands at 1563 and 1506 cm⁻¹). The type B carbonate ion is located close to the sloping faces of the PO₄ tetrahedron (IR bands at 1474 and 1406 cm⁻¹), confirming earlier inferences from polarized IR spectra.     

A Structural Investigation of La2(GeO4)O and Alkaline-Earth-Doped La9.33(GeO4)6O2

The structures of the oxyorthogermanate La₂(GeO₄)O and the apatite-structured La_9.33(GeO₄)₆O₂ have been refined from powder neutron diffraction data. La₂(GeO₄)O crystallizes in a monoclinic unit cell (P2₁/c) and is cation stoichiometric in contrast to previous reports. La_9.33(GeO₄)₆O₂ crystallizes in a hexagonal unit cell (P6₃/m) and the powder diffraction data show anisotropic peak broadening that is observed in electron diffraction patterns as incommensurate diffuse spots at hkq reciprocal planes (with q=1.6-1.7) and can be attributed to a correlated disorder in the “apatite channels”. This compound was doped up to a nominal composition close to M₂La₈(GeO₄)₆O₂ with M=Ca, Sr, Ba. The dopant ions preferentially occupy the 4f sites as the number of La vacancies decreases. The measured ionic conductivity of La_9.33(GeO₄)₆O₂ is about 3 orders of magnitude larger than for La₂(GeO₄)O at high temperatures and decreases with increasing dopant content from the highest value of about 0.16 S cm⁻¹ at 1160 K.