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.     

电流密度对钙磷沉积层组成和结构的影响(英文)

用X射线衍射、激光拉曼光谱以及等离子体原子发射光谱等技术研究了电化学沉积钙磷陶瓷过程中 ,电流密度对电沉积层组成和结构的影响 .实验表明阴极表面得到的沉积物是几种钙磷盐组成的混合物 ,且其成份随电流密度的改变而发生较大的变化 .在电解液温度为 75℃条件下 ,当控制电流密度较低时 ,沉积层主要由CaHPO4· 2H2 O (DCPD)和Ca8H2 (PO4) 6· 5H2 O (OCP)组成 ;随着电流密度的增加 ,阴极表面逐渐生成Ca3 (PO4) 2 ·nH2 O (TCP)和Ca10 (PO4) 6(OH) 2 (HAP) .当电流密度大于 5mA/cm2 时 ,电沉积层的主要成份为羟基磷灰石 (HAP) .     

电沉积羟基磷灰石/TiO2复合涂层

结合强度;电沉积羟基磷灰石/TiO2复合涂层     

桑蚕丝素蛋白初始结构对其矿化作用的影响

以碱金属离子诱导桑蚕丝素蛋白溶液发生构象转变, 研究了蛋白质初始结构对其矿化作用的影响. FT-IR, XRD和SEM等测试结果显示, 未经任何处理的桑蚕丝素蛋白溶液矿化后形成片状复合物, 其无机相以二水磷酸氢钙(DCPD)为主; 而经过K^＋和Na^＋金属离子处理后, 桑蚕丝素溶液的结构由无规线团/螺旋构象向β-折叠发生转变, 矿化后成纤维状, 并相互结合呈现纳米级的三维多孔结构, 其无机相以热力学稳定的羟基磷灰石(HA)为主. 可以认为, 丝素蛋白结构转化为较伸展的β-折叠后, 使得更多的亲水基团暴露在外面, 在丝素蛋白分子不断凝聚成纤过程中, HA结晶快速生长并附着在这些微纤上, 最终形成纤维状的丝素蛋白/HA复合物. 该结果为阐明蛋白质的生物矿化过程及其调控机理提供了理论依据, 同时可以从矿化复合物的形成来反映这些微量元素可能对骨组织形成的影响, 为临床骨组织的修复提供一定的参考.     

Titanium‐implanted CaTiO3 films and their changes in Hanks' solution

Titanium‐implanted CaTiO₃ film was prepared and then characterized by x‐ray photoelectron spectroscopy (XPS) and Rutherford backscattering spectrometry (RBS) before and after immersion in Hanks' solution for 7 days. An as‐prepared specimen contained a small amount of Ar implanted during sputtering, although the pressure was as low as 10^?4 Torr. Even though Ar convolution increased with an increase in the relative Ti ion dose, most of the convoluted Ar was not from the Ar gas used for Ti ion production but rather was from the Ar gas used for sputtering the CaTiO₃. During Ti implantation, the CaTiO₃ films were ion‐etched by Ti ions. The composition of the CaTiO₃ film was not changed to any great degree by the Ti implantation, however its properties changed considerably. After immersion in Hanks' solution, the thickness of the specimen not implanted with Ti decreased the most whereas the [Ca]/[P] ratio, which was nearly unity before exposure, decreased significantly, becoming 0.23 on the Ti‐implanted specimen prepared at 200 W and 0.13 on the Ti‐implanted specimen prepared at 50 W. It was also observed by XPS that the ratio [Ca]/[P] was ～1.9 for all Ti‐implanted specimens after immersion in Hanks' solution for 7 days. Judging from the binding energies of Ca 2p_3/2 and P 2p electrons and the [Ca]/[P] ratio, it was suggested that a hydroxyapatite‐like substance had formed on the surfaces of the Ti‐implanted specimens after immersion in Hanks' solution. Copyright © 2003 John Wiley & Sons, Ltd.     

明胶中α组分含量对明胶/羟基磷灰石复合材料力学性能的影响

选用α组分含量分别为20.5%,41%和50%的A、B、C 3种明胶作为原料,采用同时加入法制备了明胶/羟基磷灰石(HAP)复合材料.通过对干态复合物膜拉伸性能的测试和对比,发现,明胶α组分含量的变化对复合材料的弹性模量影响较大,而对拉伸强度和断裂伸长率的影响则相对较小,但总的来说,三者均随α组分含量的增加而增大.其中,α组分含量最高的复合物C的拉伸强度为86.40 MPa,弹性模量为2682.35 MPa,断裂伸长率为8.65%.另外,对复合物C基本性质的表征结果表明,该材料具有类似于自然骨的组成和结构性质,因此有望成为一种具有优异力学性能的骨替代材料.     

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     

PHBV/HA骨修复材料的研究

利用硝酸钙与磷酸钠的水溶液制备羟基磷灰石(HA)，同时在HA生成过程中与聚羟基丁酸一戊酸酯(PHBV)复合，探索了HA增强PHBV使之适于作为骨修复材料的一种新途径。结果表明，HA的均匀分散增进了复合材料中两相问的相互结合，能明显地提高复合材料的力学性能。     

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.