高硅沸石骨架结构及其稳定性的模拟计算(Ⅱ)

应用晶格能极小化技术计算了二十一种高硅沸石的骨架晶格能，计算结果与二氧化硅致密相比较，发现这些高硅沸石彼此间的晶格能相差很小（〈３７ｋＪ／ｍｏｌ），与α－石英相差３０￣６７ｋＪ／ｍｏｌ。分析这些高硅沸石的ＸＲＤ数据发现，在它们的结构中包含很短的Ｓｉ－Ｏ键长（０．１４３１ｎｍ），很长的Ｓｉ－Ｐ键长（０．１８６２ｎｍ），Ｏ－Ｓｉ－Ｏ键角分布范围大（７７．５１￣１３１．８８°），Ｓｉ－Ｏ－Ｓｉ键角平均在     

高硅沸石骨架结构及其稳定性的模拟计算(Ⅱ)

应用晶格能极小化技术计算了二十一种高硅沸石的骨架晶格能，计算结果与二氧化硅致密相比较，发现这些高硅沸石彼此间的晶格能相差很小（＜３７ｋＪ／ｍｏｌ），与α石英相差３０～６７ｋＪ／ｍｏｌ．分析这些高硅沸石的ＸＲＤ数据发现，在它们的结构中包含很短的ＳｉＯ键长（０１４３１ｎｍ），很长的ＳｉＯ键长（０１８６２ｎｍ），ＳｉＯＯ键角分布范围大（７７５１～１３１８８°），ＯＳｉＳｉ键角平均在１５３°左右并且具有更大的分布范围（１２０～１８０°）．量子化学ＰＭ３计算结果表明，ＯＳｉＳｉ键角由１１４°变化至１８０°而引起的能量改变很小（仅１７４３ｋＪ／ｍｏｌ），当ＯＳｉＳｉ键角为１３５４°时能量最低．     

三羰基环戊二烯基钼负离子与1，3－二卤丙烷的反应

三羰基环戊二烯基钼负离子与１，３－二卤丙烷在一缩二乙二醇二甲醚介质中反应，生成环卡宾配合物ＣｐＭｏＸ（ＣＯ）＿２ＣＯ（ＣＨ＿２）＿２ＣＨ２（Ｘ＝Ｂｒ，Ｉ）．硅桥连双环戊二烯基三羰基钼负离子与１，３－二卤丙烷顺利地进行类似反应，生成相应的硅桥连双［环卡宾钼配合物］──Ｅ［Ｃ＿５Ｈ＿４ＭｏＸ（ＣＯ）＿２］ＣＯ（ＣＨ＿２）＿２ＣＨ＿２］＿２（Ｅ＝Ｍｅ＿２Ｓｉ，Ｍｅ２ＳｉＳｉＭｅ＿２，Ｍｅ２ＳｉＯＳｉＭｅ＿２）．化合物硅氧硅桥联二茂二钼环卡宾配合物１１的晶体结构经Ｘ射线衍射测定，晶体属三斜晶系，Ｐ１空间群，晶体学数据：ａ＝０．８１８８（１）ｎｍ，ｂ＝１．０４５（３）ｎｍ，ｃ＝２．３２５２（４）ｎｍ，α＝９４．１４（２）°，β＝９４．０９（１）°，γ＝１０２．４８（２）°，Ｖ＝１．９３０６ｎｍ￣３，Ｚ＝２，Ｄ＿ｃ＝１．８５４ｇ／ｃｍ￣３。     

配合物E（η~5－Me_3SiC_5H_3）_2［Fe（CO）］_2（μ－CO）_2的合成与结构

硅桥连配体Ｅ（Ｍｅ_３ＳｉＣ_５Ｈ_４）_２（Ｅ＝ＳｉＭｅ_２（Ⅰ），Ｍｅ_２ＳｉＯＳｉＭｅ_２（Ⅱ），以下同）与Ｆｅ（ＣＯ）_５在二甲苯中加热反应，生成配合物Ｅ（η~５Ｍｅ_３ＳｉＣ_５Ｈ_３）_２［Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２．~１ＨＮＭＲ和四圆Ｘ射线衍射分析表明化合物１、２皆为顺式构型．反应过程中存在严重的脱硅基现象。１、２皆为单斜晶系，Ｐ２_１／ｍ空间群。１：α＝０．７３５９（３）ｎｍ，ｂ＝１．９４０９（１）ｎｍ，ｃ＝０．９３８３（５）ｎｍ，β＝９９．７１（４）°，Ｚ＝２；２：α＝０．６７４３（５）ｎｍ，ｂ＝２．２６３５（５）ｎｍ，ｃ＝１．０８０２（１）ｎｍ，β＝１０８．１（２）°，Ｚ＝２。     

硅锑钼杂多酸·罗丹明B缔合物的共振散射光谱研究及其应用

在０．０４ｍｏｌ／Ｌ Ｈ２ＳＯ４介质中,ＳｉＯ＾２－３、Ｓｂ（Ⅲ）和ＭｏＯ＾２－４形成Ｓｉ－Ｓｂ－Ｍｏ三元杂多酸;调节酸度至０．２２ｍｏｌ／Ｌ Ｈ２ＳＯ４加入罗丹明Ｂ生成四元缔合物。该缔合物在６００ｎｍ处产生一灵敏的共振散射峰。据此建立了一个测定２－４０ｎｇ／ｍＬ Ｓｉ的共振散射光谱分析新方法,用于钢样中硅的测定,结果满意。     

采用红外漫反射光谱研究纳米Si3N4的表面结构

采用付利叶红外漫反射光谱对激光法制取的具有不同化学组成的纳米Ｓｉ３Ｎ４粉（１５４－３０ｎｍ）的表面结构，室表面氧化及热稳定性进行了研究，结果表明新鲜的富氮粉体表面主要为硅胺基（Ｓｉ３－ｘＮＨｘ，ｘ＝１－３）结构，粉体暴露空气后硅胺基会与空气中的水分子反应形成硅醇基（ＳｉＯＨ）结构，具有不同组成的粉体随粉中氮含量的增大粒子表面硅胺基量也增加；富硅粉体表面硅胺基较少，其氧化主要为表面硅原子与空气中氧原     

（四甲基二硅撑）二（3－三甲硅基环戊二烯基）四羰基二铁及其相关化合物的合成及结构

１，２－二（三甲硅基环戊二烯基）四甲基二硅烷与Ｆｅ（ＣＯ）_５在二甲苯中于１０５～１１０℃反应除分离到少量标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（５）外，主要是生成了脱Ｍｅ_３Ｓｉ基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（１）及１的热重排异构体［Ｍｅ_２ＳｉＣ５Ｈ４－Ｆｅ（ＣＯ）_２］_２（２）．将５的二甲苯溶液加热回流１８ｈ，则转化为其异构体［Ｍｅ_２Ｓｉ（Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２（６）．脱硅基发生在由相应反应物制备５的过程中。且脱硅基是与反应物中（Ｍｅ_２ＳｉＳｉＭｅ_２）桥的存在有关．５的晶体结构经Ｘ射线衍射测定属单斜晶系，Ｐ２_１／ｍ空间群，晶体学数据：ａ＝０．６７８０（１）ｎｍ，ｂ＝２．２３０３（９）ｎｍ，ｃ＝０．９９８８（１）ｎｎ，；β＝９８．９６（１）°，Ｖ＝１．４９６０ｎｍ~３．Ｚ＝２，Ｄ_ｃ＝１．３６ｇ／ｃｍ~３．     

红外激光诱导SiO2薄膜生长的氧化动力学研究

在较低基底温度（室温至～２００℃）下，用μ０．６μｍ ＣＷ ＣＯ２激光在硅（１００）表面生成ＳｉＯ２薄膜，研究了反应气配比（Ｏ２／Ｎ２），基底温度、激光强度、激光辐照时间等实验条件对ＳｉＯ２薄膜形成的影响，探讨了红外激光助长的硅表面氧化反应动力学过程，认为在薄层氧化区域（＜３０ｎｍ）存在反应诱导期。     

REGaSi的合成、结构及Ga-Si成键网络

用电弧熔炼法合成了系列化合物ＲＥＧａＳｉ,采用粉末Ｘ射线衍射方法测定了化合物ＳｍＧａＳｉ的晶体结构,获得其晶体学及结构修正参数为;四方晶系,ＬａＰｔＳｉ类型,（１０９）Ｉ４１ｍｄ,Ｍｒ＝２５０．０,ａ＝０．４１３４（３）ｎｍ,ｃ＝１．４２２（２）ｎｍ,Ｖ＝０．２４３０（５）ｎｍ＾３,Ｚ＝４,Ｄｘ＝６．４６４ｇ．ｃｍ＾－３,Ｆ（０００）＝４２８,Ｔ＝２９６Ｋ。     

光电化学刻蚀n^＋—Si的电致发光

ｎ＋－Ｓｉ在ＨＦ水溶液中经光电化学刻蚀形成的微米级多孔硅（ＰＳ）具有较好的电致发光（ＥＬ）性能，其发光光谱的波长范围约在５００～８００ｎｍ之间，阴极ＥＬ的波长和强度均随调制电位可逆变化；在酸性溶液中，发光强度较大，光淬灭过程也较中性溶液为慢．与ｎ－－Ｓｉ的结果类似，ＰＳ的制备电位也决定性地影响着ＥＬ的强度．光淬灭前的伏安行为表明，除Ｓ２Ｏ２－３和Ｈ＋还原外，可能还涉及ＰＳ表面化合物的转化．对能带图进行了讨论．     

High-Performance Liquid Chromatography of Copper,Mercury, Nickel,and Cadmium Bisdibenzyldithiocarbamate Complexes

Abstract

High-performance liquid chromatographic separations of Cu (II), Hg(II), Ni(II), and Cd(II) bisdibenzyldithiocarbamates at nanogram levels by adsorption chromatography on silica gel were reported. Lichrosorb Si 60 (10 um) was used as the stationary phase and benzene-cyclohexane mixtures as the mobile phase.     

Structural stability of quaternary ACuFeS2 (A = Li, K) phases: a computational approach

At ambient conditions, the quaternary sulfides LiCuFeS(2) and KCuFeS(2) present totally different crystal structures: while LiCuFeS(2) crystallizes in a trigonal CaAl(2)Si(2)-type structure, a tetragonal ThCr(2)Si(2)-like structure is found for KCuFeS(2). In this work, we present a computational study describing first the changes in the structural preference of the ACuFe(2) phases as a function of the alkali ion and second, the structural stability of the CuFeS(2) phases obtained by electrochemical removal of the alkali cations from the two ACuFeS(2) compounds. A high copper mobility is found to be responsible for the observed metastability of the layered trigonal CuFeS(2) phase obtained by delithiation of LiCuFeS(2). In contrast, the tetragonal CuFeS(2) structure obtained removing potassium from KCuFeS(2) is predicted to be stable, both from the kinetic and thermodynamic points of view. The possibility of stabilizing mixed Li(x)Cu(1-x)FeS(2) phases with a ThCr(2)Si(2)-type structure and the mobility of lithium in these is also explored.     

Electroless deposition of gold thin films on silicon for surface-enhanced infrared spectroelectrochemistry

Electroless (or chemical) deposition technique has been used in preparing Au island film electrodes on Si for in situ infrared spectroscopic studies of the electrochemical interface in attenuated total reflection mode. Owing to surface-enhanced infrared absorption (SEIRA) effect, absorption bands of molecules adsorbed on the chemically deposited films were one order of magnitude as large as those observed on smooth Au electrode surfaces. Although the enhancement factor was identical to that observed on vacuum evaporated Au island films, this simple method is superior to vacuum evaporation method with respect to the adhesion of the film, surface contamination, reproducibility, and cost.     

Synthesis and Electron-Beam Polymerization of 1-Propenyl Ether Functional Siloxanes

Abstract

A novel synthesis of 1-propenyl ether functionalized siloxanes has been achieved by the controlled, rhodium-catalyzed, chemoselective hydrosilation of 1-allyloxy-4(1-propenoxy)butane (APB) with various H-functional siloxanes. Chemoselective hydrosilation using a variety of Si—H functional siloxanes proceeds exclusively at the allyl ether group of the APB without participation at the 1-propenyl ether group. The electron-beam-induced cationic polymerization of these monomers in the presence of a diaryliodonium salt was studied and found to take place very rapidly and at very low radiation doses.     

Physicochemical characterisation of lead titanate solutions applied to the processing of thin films

A new sol-gel method, in which dihydroxy alcohols are used as solvents, is described for the preparation of lead titanate thin films. Infrared spectroscopy and measurements of viscosity are used to study the reaction mechanisms involved in the formation of polymerized solutions. Crack-free lead titanate layers with thickness 0.5 µm are obtained from these solutions, on Pt/TiO₂/Si substrates, by spin-coating and subsequent heat treatments. The formation of the perovskite and the microstructure of these films are monitored by X-ray diffraction, thermogravimetry analysis, differential thermal analysis and scanning electron microscopy.     

A novel rapid method for preparation of sample solution for chemical characterisation of titanium minerals by atomic spectrometry

A new rapid decomposition and dissolution method with a mixture of sodium di-hydrogen orthophosphate and di-sodium hydrogen orthophosphate as a novel flux is described. The minerals are fused with (1:1) mixture of the above salts (flux) and the melt is dissolved in distilled water. The solution is diluted to desired volume depending on the instrumental technique used for determination. ICP-OES is used for the determination of Al, Ca, Mg, Cr, V, Si, Fe and Ti without interference from titanium, iron and sodium phosphate (introduced as flux). All the elements except Si and V are also determined by AAS. The use of nitrous oxide–acetylene flame eliminates the depression due to titanium in the measurement of Mg, Mn, Cr and Fe in air–acetylene flame. Synthetic mixture conforming to ilmenite and rutile composition are analyzed by ICP-OES and AAS to check the validity of the method. The results are in good agreement. The proposed method has been applied to natural samples and the results are evaluated against the established decomposition method using potassium bisulphate. Both ICP-OES and AAS yielded comparable results. The R.S.D. of the proposed method in case of ICP-OES varies from 0.5 to 2%, whereas for AAS it varies from 1.5 to 3% for different elements (n = 5). The novelty of the proposed sample decomposition lies in its simplicity, ease and speed of fusion with minimal skills besides being eco-friendly unlike the reported tedious complicated decomposition procedures involving variety of fluxes and lot of hazardous chemicals.     

新型洗涤剂用沸石MAP的合成及其性能表征

在ＳｉＯ_２－Ａｌ_２Ｏ_３－Ｎａ_２Ｏ－Ｈ_２Ｏ体系中,采用加入晶种的方法水热合成出新型洗涤剂用沸石－ＭＡＰ。其硅铝比（Ｓｉ／Ａｌ）在 １．０７－１．１３之间,平均晶粒直径小于０．４μｍ,钙离子交换容量为２９０～３１３ ｍｇＣａＣＯ_３／ｇ（干沸石）,非离子表面活性剂的吸附量在 ８３～ １００ｇ ｏｉｌ／１００ｇ（沸石）之间。本文着重考察了影响合成 ＭＡＰ沸石的因素,确定了ＭＡＰ沸石会成的最佳范围,并对其物理化学性质进行了表征。     

Das Homogenitätsgebiet des MoSi2

Zusammenfassung Es sind Versuche ausgeführt worden, um die untere Grenze für den Si-Gehalt im Homogenitätsgebiet von MoSi₂ zu bestimmen. Diese Grenzen wurde zu 37,4±1,1% Si bestimmt. Bis zu 36% Si im Silicid wurde immer Mo₅Si₃ neben MoSi₂ röntgenographisch nachgewiesen. Diese Grenze wird von Bindemittelresten aus Äthylsilicat oder Montmorillonit sowie durch Glühen in Wasserstoff bis 1750°C nicht in meßbarem Betrag beeinflußt. In dem gesamten Probematerial konnten auch keine Veränderungen weder der Gitterkonstanten noch der relativen Intensitäten der Röntgenreflexe der MoSi₂-Phase beobachtet werden.     

The Photochemical Study of HSA and BSA with Resonance Light-Scattering and Fluorescence Spectra

In recent years, people have paid close attention to the physiological harms induced byultraviolet (UV) irradiation. The serum albumin, which constitutes 60% of blood plasma,has very important physiological functions. Therefore, to study their photochemicalreaction is of great significance. The metal ions, little molecules and medicines etcinteracting with HSA or BSA have been reported ','*"', but it has not been repoFted aboutusing RLS to study the photochemical reaction of HSA or BSA.…     

Fünf Jahre organische Ultramikro-Elementaranalyse in einem Industrielaboratorium

Zusammenfassung Seit mehreren Jahren haben sich im Untersuchungslaboratorium der BASF entwickelte Methoden zur Bestimmung von C, H, N, O, S, P, Si und den Halogenen mit Einwaagen unter 1 mg im Routineeinsatz bewährt. Die Methoden sind kaum aufwendiger als die bisher verwendeten Mikromethoden und von gleicher Genauigkeit. Damit ist für Routineanalysen abermals eine Verringerung der Einwaage um eine Zehnerpotenz gelungen.

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Five years of organic ultramicro ultimate analysis in an industrial laboratory

Summary The methods developed in the research laboratory of the BASF for determining C, H, N, O, S, P, Si and the halogens, employing a sample below 1 mg, have proven their worth in routine work. These procedure are hardly more consuming than the micro methods employed previously and they exhibit the same precision. They permit the successful use of smaller samples (by one power of ten) in routine analyses.

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Herrn Professor Dr.Bernhard Timm zum 60. Geburtstag gewidmet.