Ionophoretische Trennung von ReCl62?, ReBr62? und ReO4?

Zusammenfassung Es wurde die ionophoretische Trennung von ReCl₆ ^2–, ReBr₆ ^2– und ReO₄ ^– unter Verwendung verschiedener Papiersorten untersucht. Am geeignetsten erwies sich das Papier 2045 b Gl von Schl. & Sch.

---

Summary The ionophoretic separation of ReCl₆ ^2–, ReBr₆ ^2–, and ReO₄ ^– has been examined using different kinds of paper. Best results have been obtained with the paper 2045 b Gl from Schleicher & Schüll.

---

---

Herrn Prof. G. Brauer danke ich für Förderung. Für die Überlassung von Rheniumverbindungen bin ich der Fa. W. C. Heraeus, Hanau, verpflichtet. Die Neutronenaktivierung wurde freundlicherweise von den Herren Dr. Marth und Dr. Köhler von der Reaktorstation in Garching bei München vorgenommen. Das Bundesministerium für Atomkernenergie und Wasserwirtschaft unterstützte die Untersuchung durch eine Sachbeihilfe.     

Hypervalence and the delocalizing versus localizing propensities of H 3– , Li 3– , CH 5– and SiH 5–

Lithium and silicon have the capability to form hypervalent structures, such as Li₃^– and SiH₅^–, which is contrasted by the absence of this capability in hydrogen and carbon, as exemplified by H₃^– and CH₅^– which, although isoelectronic to the former two species, have a distortive, bond-localizing propensity. This well-known fact is nicely confirmed in our DFT study at BP86/TZ2P. We furthermore show that the hypervalence of Li and Si neither originates from the availability of low-energy 2p and 3d AOs, respectively, nor from differences in the bonding pattern of the valence molecular orbitals; there is, in all cases, a 3-center-4-electron bond in the axial X–A–X unit. Instead, we find that the discriminating factor is the smaller effective size of C compared to the larger Si atom, and the resulting lack of space around the former. Interestingly, a similar steric mechanism is responsible for the difference in bonding capabilities between H and the effectively larger Li atom. This is so, despite the fact that the substituents in the corresponding symmetric and linear dicoordinate H₃^– and Li₃^– are on opposite sides of the central atom. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Isomerism of metal complexes with the boron cluster anions B10H 102? and B12H 122?

A new type of inner-sphere isomerism in coordination chemistry observed in metal complexes with boron cluster anions B _n H _n ²⁻ (n = 10, 12) is discussed. Specific structure of the closo-borohydride anions gives rise to edge and facial isomers, among which mirror isomers have been found. Examples of edge and facial isomers of metal complexes with the B₁₀H₁₀²⁻ and B₁₂H₁₂²⁻, anions obtained experimentally and studied by X-ray diffraction are considered. Analysis of their structure revealed a new type of isomerism, which was called “positional.”     

磷改性失活TS-1高效催化C5=裂解制备C2=/C3=反应的研究

发展C₅⁼催化裂解高效制乙烯和丙烯(C₂⁼/C₃⁼)技术具有重要的研究意义及工业应用价值,其核心在于高效催化剂的开发.本文发展了以失活钛硅分子筛TS-1(De-TS-1)为催化剂的C₅⁼催化裂解过程,研究发现,P改性后的De-TS-1显示出优异的催化反应性能,C₂⁼+C₃⁼选择性与单程寿命分别达77.1%和213 h,其综合催化性能优于经典的ZSM-5催化剂.进一步研究表明,De-TS-1的Br?nsted性质符合C₅⁼裂解高效裂解的基本要求,P改性可进一步降低De-TS-1中Br?nsted酸的酸密度和酸强度,从而促进了目标产物C₂⁼/C₃⁼生成的主反应,抑制了C₅     

Eine titrimetrische Bestimmung von ClO?, ClO2? und ClO3? aus einer Probe

Ohne Zusammenfassung     

Polyatomic anion versus acetonitrile in coordinating ability: structural properties of AgX-bearing 1,4-bis(2-isonicotinoyloxyethyl)piperazine (X??=?NO3?, CF3SO3?, ClO4?, BF4?, and PF6?)

Type studies on competitive polyatomic anion versus acetonitrile coordination in the self-assembly of a series of [Ag₂(X) _m (bip)(NCCH₃) _n ](X)_2−m (X⁻ = NO₃ ⁻, CF₃SO₃ ⁻, ClO₄ ⁻, BF₄ ⁻, and PF₆ ⁻; m = 0, 2; n = 0, 2, 4; bip = 1,4-bis(2-isonicotinoyloxyethyl)piperazine) were carried out. Each bip spacer acts as an N₄ tetradentate ligand and is linked to four silver(I) centers through two pyridine and two piperazine moieties, producing a double strand consisting of two 20-membered ring units. The coordinating environment around the silver(I) center is subtly determined by the competition of the polyatomic anions with acetonitrile, that is, by the Ag···NCCH₃ versus Ag···X interactions. The coordinating ability of acetonitrile is inversely proportional to the order of the coordination ability of the Hoffmeister series of polyatomic anions, NO₃ ⁻ ≫ CF₃SO₃ ⁻ > ClO₄ ⁻ > BF₄ ⁻ ≫ PF₆ ⁻.     

N4+的生成与检测

用从Nd:YAG激光器发出的波长532nm的激光(能量约为10mJ/pulse)溅射由BN、ZrN粉末分别压成的直径13mm、厚度约2～5mm的固体压片样品,生成了含氮团簇N4+。实验中,用高纯氮气为载气,辅助含氮团簇的生成并冷却激光溅射所产生的团簇。反射式飞行时间质谱仪监测反应过程证实N4+的存在,且其存在时间超过200μs。     

五元体系Li+，Na+//CO32-，SO42-，B4O72--H2O 288 K介稳相平衡研究

采用等温蒸发法研究五元体系Li⁺,Na⁺//CO₃^2-,SO₄^2-,B₄O₇^2--H₂O 288 K介稳相平衡关系,测定在288 K条件下的介稳平衡溶液中各组分的溶解度和溶液密度,根据实验数据绘制相应的介稳平衡相图及密度组成图。研究结果表明该五元体系介稳相平衡中有复盐Na₃Li(SO₄)₂·6H₂O生成,其介稳相图中有4个共饱点,9条单变量曲线,6个Li₂CO₃饱和的结晶区分别为LiBO₂·8H₂O,Na₂B₄O₇·10H₂O,Na₂CO₃·10H₂O,Na₂SO₄,Li₂SO₄·H₂O和复盐Na₃Li(SO₄)₂·6H₂O。     

PO43-掺杂Bi2O2CO3/Bi0的制备及其可见光催化性能

构建氧空位以及附着金属单质Bi(Bi⁰)是增强半导体材料光吸收性能、促进半导体光生载流子分离的有效方法。通过简单的共沉淀法及氢气热还原成功制备了PO₄^3-掺杂Bi₂O₂CO₃附着Bi⁰(Bi-P-BOC)的可见光催化剂,并对其在可见光下催化降解氧氟沙星(OFX)的性能及机理进行了研究。材料表征结果表明BOC随着PO₄^3-的均匀掺杂,可见光吸收能力增强,表面缺陷增多,比表面积增大。而随着氢气热还原,BOC表面形成Bi⁰的同时也原位构建了大量的氧空位。可见光催化性能测试表明,Bi-P-BOC可以在180 min内降解约85%的OFX,降解速率为0.013 0 min^-1,是BOC降解速率的8倍。Bi-P-BOC光催化降解机理表明其具有更好的可见光吸收能力,Bi⁰以及氧空位的存在促进了光生载流子的分离,h⁺是其...     

可见光照射下SiW12O404-/Resin光催化剂活化可见光照射下SiW12O404-/Resin光催化剂活化H2O2降解染料的研究

将杂多酸(SiW₁₂O₄₀^4-)负载到阴离子交换树脂上, 得到SiW₁₂O₄₀^4-/Resin (SWR)固相光催化剂, 在可见光的照射下, 可以有效地活化H₂O₂降解染料. 以罗丹明B (Rhodamine B, RhB)为模型化合物, 研究了不同条件下RhB的降解动力学, 以及降解过程中其UV-vis光谱及体系的总有机碳(Total Organic Carbon, TOC)变化情况, 结果表明RhB的共轭芳环结构被破坏, 矿化率为24.2%. 其它染料如孔雀绿(Malachite Green, MG)和吖啶橙(Acridine Orange, AO)等也可以被降解和矿化. 催化剂的循环实验表明SWR固相光催化剂易于分离, 并且具有良好的稳定性, 可以重复利用.     

可见光照射下SiW12O404-/Resin光催化剂活化可见光照射下SiW12O404-/Resin光催化剂活化H2O2降解染料的研究

将杂多酸(SiW₁₂O₄₀^4-)负载到阴离子交换树脂上, 得到SiW₁₂O₄₀^4-/Resin (SWR)固相光催化剂, 在可见光的照射下, 可以有效地活化H₂O₂降解染料. 以罗丹明B (Rhodamine B, RhB)为模型化合物, 研究了不同条件下RhB的降解动力学, 以及降解过程中其UV-vis光谱及体系的总有机碳(Total Organic Carbon, TOC)变化情况, 结果表明RhB的共轭芳环结构被破坏, 矿化率为24.2%. 其它染料如孔雀绿(Malachite Green, MG)和吖啶橙(Acridine Orange, AO)等也可以被降解和矿化. 催化剂的循环实验表明SWR固相光催化剂易于分离, 并且具有良好的稳定性, 可以重复利用.     

五元体系Li+/Cl-，CO32-，SO42-，B4O72--H2O 298 K相关系实验研究

Zabuye saline lake, Tibet, China, is unrivalled in the world for its high concentration of chloride, sulfate, carbonate and borate of lithium, sodium and potassium. Always at the later stage of the evaporation of brines, most sodium and potassium salts are crystallized out, so the main components of brines can be described with the Li⁺, Mg²⁺/Cl^-, SO₄^2-, CO₃^2-, B₄O₇^2--H₂O system. As a part of study on the equilibrium of this complex system, the equilibrium solubilities and phase diagram of the quinary system Li⁺/Cl^-，CO₃^2-，SO₄^2-，B₄O₇^2--H₂O at 298 K were studied by isothermal dissolution equilibrium method. In the 3-dimentional solubility diagram or its projection diagram saturated with solid LiCl, there are four crystallization fields, four univariant curves and one invariant point. At the invariant point, the saturated solid salts are LiCl·H₂O, Li₂B₄O₇·3H₂O, Li₂CO₃and Li₂SO₄·H₂O. No double salt or solid solution is formed.     

PO43-掺杂Bi2O2CO3/Bi0的制备及其可见光催化性能

构建氧空位以及附着金属单质Bi(Bi⁰)是增强半导体材料光吸收性能、促进半导体光生载流子分离的有效方法。通过简单的共沉淀法及氢气热还原成功制备了PO₄^3-掺杂Bi₂O₂CO₃附着Bi⁰(Bi-P-BOC)的可见光催化剂,并对其在可见光下催化降解氧氟沙星(OFX)的性能及机理进行了研究。材料表征结果表明BOC随着PO₄^3-的均匀掺杂,可见光吸收能力增强,表面缺陷增多,比表面积增大。而随着氢气热还原,BOC表面形成 Bi⁰的同时也原位构建了大量的氧空位。可见光催化性能测试表明,Bi-P-BOC可以在180 min内降解约85%的OFX,降解速率为0.013 0 min^-1,是BOC降解速率的8倍。Bi-P-BOC光催化降解机理表明其具有更好的可见光吸收能力,Bi⁰以及氧空位的存在促进了光生载流子的分离,h+是其光催化降解过程中的主要的活性氧物种(ROS),此外,¹O₂和·O₂^-也对降解有一定贡献。     

Die halbquantitative Bestimmung von Cl?, Br?, J?, SCN?, AsO43?, Cr2O72? und [Fe(CN)6]3?

Ohne Zusammenfassung     

Synthesis and structure of C17H22FN3O 32+ ?CuCl 42-

A new compound C₁₇H₂₂FN₃O₃ ²⁺ • CuCl₄ ^2- [pefloxacindium tetrachlorocuprate(II)], C₁₇H₂₀FN₃O₃ — 1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(4-methyl-1-piperazinyl)-3-quinoline carboxylic acid (pefloxacin, PefH) is synthesized and characterized by single crystal X-ray diffraction technique. The crystal structure of the compound contains one PefH₃ ²⁺ cation and one CuCl₄ ^2- anion. The supramolecular architecture of the crystal is determined.     

Crystal structure of a new compound C17H22FN3O32+·ZnCl42-

A new compound C₁₇H₂₂FN₃O₃ ²⁺ ZnCl₄ ² (pefloxacindium tetrachlorozincate(II)), C₁₇H₂₀FN₃O₃ 1-ethyl-N-methyl-6-fluoro-1,4-dihydro-4-oxo-7-(4-methyl-1-piperazinyl)-3-quinoline carbonic acid (PefH, pefloxacin) is synthesized, and its crystal structure is determined. The crystal contains PefH₃ ²⁺ and ZnCl₄ ²⁻ ions. The supramolecular architecture of the crystal is analyzed.     

五元体系Li＋, K＋//, CO32- ,SO42- , B4O72- -H2O在288 K时的介稳相平衡研究

采用等温蒸发法研究了五元体系Li^＋, K^＋//, , -H₂O 在288 K时的介稳相平衡关系, 测定了该五元体系在288 K条件下的介稳平衡的溶解度和溶液密度, 根据实验数据绘制了相应的介稳平衡相图和水图. 相平衡研究结果表明该五元体系介稳相平衡中有复盐K₂SO₄•Li₂SO₄生成, 其介稳相图(Li₂CO₃饱和)有4个共饱和点, 9条单变量曲线, 6个Li₂CO₃饱和的结晶区分别为LiBO₂•8H₂O, K₂B₄O₇•4H₂O, K₂CO₃•3/2H₂O, K₂SO₄, Li₂SO₄•H₂O和复盐 K₂SO₄•Li₂SO₄.     

Crystal structure of pefloxancindium tetrabromidozinkate C17H22FN3O 32+ · ZnBr 42?

A new compound, namely pefloxancindium tetrabromidozincateC₁₇H₂₂FN₃O₃²⁺ · ZnBr₄²⁺ where C₁₇H₂₀FN₃O₃ is 1-ethyl-N-methyl-6-fluoro-1,4-dihydro-4-oxo-7-(4-methyl-1-piperazinyl)-3-quinoline carboxylic acid (PefH, pefloxacin), has been synthesized and its crystal and molecular structure has been solved. It contains PefH₃²⁺ and ZnBr₄²⁻ ions. The latter is a slightly distorted tetrahedron. The supramolecular architecture of a crystal has been analyzed.     

用于痕量监测Zr4+、Cr2O72-、Fe3+、HPO42-和指纹识别的功能化Eu3+/Tb3+配位聚合物荧光探针的构筑

采用芳香族π共轭及含氮原子有机连接剂,合成同构铽、铕发光配位聚合物(CPs){[Eu(PLIA)_1.5(H₂O)₂]·H₂O}_n (1)和{[Tb(PLIA)_1.5(H₂O)₂]·H₂O}_n (2),其中H₂PLIA=5-((吡啶-4-基甲基)氧基)苯-1,3-二甲酸。对合成的配合物进行了结构测定、表征和荧光痕量识别实验研究。2个同构配合物具有理想的三维框架结构,π…π堆积及氢键等弱相互作用增强了其化学稳定性;表征显示配位聚合物1和2具有良好的荧光性质、结晶性、热力学稳定性及结构完整性,可作为荧光传感的材料。1和2对水溶液中的Zr⁴⁺、Cr₂O₇^2-和Fe³⁺、HPO₄^2-具有选择性好、灵敏度高的荧光识别能力,其检出限分别为0.139 μmol·L^-1(1,Zr⁴⁺)、0.626 μmol·L^-1(1,Cr₂O₇^2-)、0.430 μmol·L^-1(2,Fe³⁺)、1.36 μmol·L^-1(2,HPO₄^2-)。探究了1和2作为探针的荧光猝灭机理。更有趣的是,1和2具有指纹识别性能,其荧光指纹纹路清晰连贯,细节明显,可被清晰观察。