Crystallization of ultraphosphates via the gas phase. The crystal structures of FeP4O11, ZnP4O11 and CdP4O11

The new ultraphosphates FeP₄O₁₁, ZnP₄O₁₁ and CdP₄O₁₁ of the CuP₄O₁₁ structure type were synthesized from the corresponding meta- or polyphosphates and P₄O₁₁. Crystallization via the gas phase has been achieved at elevated temperatures using a mixture of P (3 mg) and I₂ (50 mg) as mineralizer. The crystal structure consists of a two-dimensional phosphate network, built from four crystallographically independent 10-membered polyphosphate rings. Each ring contains four secondary and six tertiary PO₄-groups. Two crystallographically independent metal sites showing sixfold coordination by terminal oxygen atoms are located inbetween the phosphate layers. FeO₆-octahedra (2.028(3) Å < d̄ FeO₆ < 2.268(3) Å) and ZnO₆ octahedra (2.002(2) Å < d̄ ZnO₆ < 2.256(2) Å) exhibit slightly larger radial distortion than the CdO₆-octahedra (2.215(7) Å < d̄ CdO₆ < 2.383(3) Å).     

Penkvilksite‐2O: Na2TiSi4O11·2H2O

The crystal structure of synthetic penkvilksite‐2O, disodium titanium tetrasilicate dihydrate, Na₂TiSi₄O₁₁·2H₂O, a microporous titanosilicate, confirms the major features of a previous model that had been obtained by order–disorder (OD) theory from the known structure of penkvilksite‐1M. An important difference from the previous model involves the hydrogen bonding of the water molecule which, on the basis of a Raman spectrum and the finding of only one of the two H atoms, is proposed to be disordered about a fixed O–H direction. The structure of penkvilksite‐2O is based on (100) silicate layers linked by isolated TiO₆ octahedra to form a heteropolyhedral framework. The layer is strongly corrugated, based on interlaced spiral chains, and is crossed by two different channels that have an effective channel width of about 3 Å.     

η-Mo4O11 und Mg2Mo3O8: eine neue Synthese und Verfeinerung ihrer Kristallstrukturen

η-Mo₄O₁₁ and Mg₂Mo₃O₈: a New Way of Synthesis and Refinement of their Crystal Structures Mg₂Mo₃O₈ was obtained by solid state reaction of MgI₂ and MoO₃ (1:1) at 200°C and subsequent crystallization at 800°C. Under the same conditions, ZnI₂ and MoO₃ only yielded rather impure Zn₂Mo₃O₈; however, when ZnI₂ or CdI₂ and MoO₃ were taken in a molar ratio of 1:2, well crystallized η-Mo₄O₁₁ was obtained. The known crystal structures of Mg₂Mo₃O₈ and η-Mo₄O₁₁ were refined with new X-ray diffraction data (R = 0.030 and 0.059, respectively). The kind of twinning of monoclinic η-Mo₄O₁₁ is discussed.     

MgSO4·11H2O and MgCrO4·11H2O based on time‐of‐flight neutron single‐crystal Laue data

Hexaaquamagnesium(II) sulfate pentahydrate, [Mg(H₂O)₆]SO₄·5H₂O, and hexaaquamagnesium(II) chromate(II) pentahydrate, [Mg(H₂O)₆][CrO₄]·5H₂O, are isomorphous, being composed of hexaaquamagnesium(II) octahedra, [Mg(H₂O)₆]²⁺, and sulfate (chromate) tetrahedral oxyanions, SO₄²⁻ (CrO₄²⁻), linked by hydrogen bonds. There are two symmetry‐inequivalent centrosymmetric octahedra: M1 at (0, 0, 0) donates hydrogen bonds directly to the tetrahedral oxyanion, T1, at (0.405, 0.320, 0.201), whereas the M2 octahedron at (0, 0, ) is linked to the oxyanion via five interstitial water molecules. Substitution of Cr^VI for S^VI leads to a substantial expansion of T1, since the Cr—O bond is approximately 12% longer than the S—O bond. This expansion is propagated through the hydrogen‐bonded framework to produce a 3.3% increase in unit‐cell volume; the greatest part of this chemically induced strain is manifested along the b* direction. The hydrogen bonds in the chromate compound mitigate ∼20% of the expected strain due to the larger oxyanion, becoming shorter (i.e. stronger) and more linear than in the sulfate analogue. The bifurcated hydrogen bond donated by one of the interstitial water molecules is significantly more symmetrical in the chromate analogue.     

磁性Fe3O4@SiO2@CS镉离子印迹聚合物的制备及吸附性能

以SiO2包覆的纳米Fe3O4为载体, 壳聚糖(Chitosan, CS)为功能配体, γ-缩水甘油醚氧丙基三甲氧基硅烷为交联剂, 制备了磁性Fe3O4@SiO2@CS镉离子印迹聚合物(Magnetic ion-imprinted polymer, M-IIP). 采用扫描电镜和红外光谱对该磁性印迹聚合物进行了表征. 结果表明, 壳聚糖在环氧基硅烷交联作用下, 实现了印迹壳层在磁性Fe3O4表面的接枝, 该印迹材料是边长为60~120 nm的立方体. 吸附性能实验表明, M-IIP对Cd(Ⅱ)的吸附符合一级动力学吸附模型; M-IIP对Cd(Ⅱ)/Cu(Ⅱ), Cd(Ⅱ)/Zn(Ⅱ), Cd(Ⅱ)/Pb(Ⅱ)和Cd(Ⅱ)/Hg(Ⅱ)的相对选择系数分别为2.92, 3.43, 8.97和9.20. 原子吸收光谱检测结果表明, 该磁性Fe3O4@SiO2@CS离子印迹聚合物可用于水溶液中Cd(Ⅱ)的分离, Cd(Ⅱ)回收率在98%以上.     

Dimorphie von SrTa4O11 - ein Schritt von der tetragonalen Bronzestruktur zur Struktur von CaTa4O11

Dimorphism of SrTa₄O₁₁–a Step from the Tetragonal Structure of Bronzes to the Structure of CaTa₄O₁₁ Hexagonal SrTa₄O₁₁ is a new modification and isostructural with CaTa₄O₁₁. It was obtained by heating the already known SrTa₄O₁₁ in a chlorine atmosphere at 1000–1100°C. The Guinier powder pattern could be indexed with the following hexagonal unit cell: a = 6.25 Å; c = 12.33 Å. In air at 1180°C SrTa₄O₁₁(hex.) changes into the well-known TTB-modification (corresponding to the tetragonal tungsten bronzes). The transition of SrTa₄O₁₁(TTB) to SrTa₄O₁₁(hex.) was only observed in the presence of a transporting agent (Cl₂) or a mineralizer (melt of B₂O₃) at temperatures below 1100°C. This transition could not be achieved by means of a solid state reaction. In a (Ca, Sr) Ta₄O₁₁ solid solution with at least 78 At.-% Ca the hexagonal form could be stabilized even at temperatures where otherwise the TTB-modification occurred.