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61.
R. Miletich 《Monatshefte für Chemie / Chemical Monthly》1995,126(4):417-430
Summary The crystal structure investigations of hydrothermally synthesized Na2[Zn2(TeO3)3]·3H2O (NZT) and Na2[Co2(TeO3)3]·3H2O (NCT) using single-crystal X-ray diffraction methods revealed a microporous framework structure of hexagonal symmetry with tubular channels running parallel to the c-axis (zemannite type). The statistically occupied sites of the Na+ ions and H2O molecules within the channels as well as the channel dimensions indicate a possible zeolitic behaviour of the compounds. Thermoanalytical investigations ofNZT show an irreversible breakdown of the framework already atT=533 K caused by complete dehydration. A reversible rehydration was solely observed for partially dehydratedNZT (T493 K); a remarkable ion exchange rate from alkali-chloride solutions was observed only for Li+. Both the rehydration and the ion exchange properties are characterized by relatively long reaction times. The relatively poor zeolitic properties compared to typical zeolitic compounds could be related to the stereochemical activity of the lone-pair electrons of the Te4+ atoms which claim a certain volume within the channels and constrict the effective channel dimension to a free diameter of approximately 2.5 Å.
Die synthetischen zeolithartigen Tellurite Na2[Me 2(TeO3)3]·3H2O (Me=Zn, Co): Kristallstruktur, De- und Rehydratisierung und Ionenaustauschvermögen
Zusammenfassung Die Kristallstrukturuntersuchungen mittels Röntgen-Einkristalldiffraktionsmethoden von hydrothermal dargestelltem Na2[Zn2(TeO3)3]·3H2O (NZT) und Na2[Co2(TeO3)3]·3H2O (NCT) ergaben eine zeolithartige Gerüststruktur hexagonaler Symmetrie mit parallel zur c-Achse angeordneten röhrenartigen Kanälen (Zemannittyp). Die statistisch besetzten Punktlagen der Na+-Atome und H2O Moleküle innerhalb der Kanäle wie auch die Kanaldimensionen selbst weisen auf mögliche zeolithische Eigenschaften der Verbindungen hin. Thermoanalytische Untersuchungen anNZT ergaben einen irreversiblen Zusammenbruch der Gerüststruktur bereits beiT=533 K durch vollständige Entwässerung. Eine reversible Rehydratisierung wurde nur für partiell entwässertesNZT (T493 K) beobachtet; ein nennenswerter Ionenaustausch aus Alkalichlorid-Lösungen konnte nur für Li+ bestimmt werden. Sowohl die Rehydratisierung als auch das Ionenaustauschvermögen sind durch relativ lange Reaktionszeiten charakterisiert. Die im Vergleich zu typisch zeolithischen Verbindungen relativ schlechten zeolithischen Eigenschaften konnten auf die stereochemische Aktivität der einsamen Elektronenpaare der Te4+ Atome zurüchgefürt werden, die einen gewissen Platz innerhalb der Kanäle beanspruchen und den effektiven freien Durchmesser der Kanäle auf etwa 2.5 Å einengen.相似文献
62.
Conditions were found, under which an anomalous relationship should be observed in the energies of sequential ionization of molecules ("anomalous" molecules) such that a subsequent potential (In+1) is less than the preceding potential (In). These conditions are a function of the electronic vibrational instability of molecules or their ions upon change in the number of electrons in the system. An interrelationship was found with the previously proposed concept of effective electron—electron attraction in molecular systems.Institute of Physiologically Active Compounds, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 738–741, March, 1992. 相似文献
63.
S. Kulmala M. HåkanssonA.-M. Spehar A. NymanJ. Kankare K. LoikasT. Ala-Kleme J. Eskola 《Analytica chimica acta》2002,458(2):271-280
Heterogeneous and homogeneous immunoassays of human thyroid stimulating hormone (hTSH) were developed on immunometric basis using aromatic Tb(III) chelates as electrochemiluminescent labels and varied types of disposable oxide-covered aluminum electrodes as the solid phase of the immunoassays. The long luminescence lifetime of the present labels allows the use of time-resolved electrochemiluminescence detection and provide the low detection limits of these labels and, thus, sensitive immunoassays. The primary antibody of immunometric immunoassays was coated upon aluminum oxide surface by physical absorption. In homogeneous immunoassays using 66 μl cell and 15 min incubation time, a linear calibration range of 0.25-324 μU/ml was obtained by applying only a single cathodic excitation pulse in the detection step of the assay. 相似文献
64.
Jonathan D. Woodward 《Journal of solid state chemistry》2005,178(9):2922-2926
The reaction of UO3 and TeO3 with a KCl flux at 800 °C for 3 days yields single crystals of K4[(UO2)5(TeO3)2O5]. The structure of the title compound consists of layered, two-dimensional sheets arranged in a stair-like topology separated by potassium cations. Contained within these sheets are one-dimensional uranium oxide ribbons consisting of UO7 pentagonal bipyramids and UO6 tetragonal bipyramids. The ribbons are in turn linked by corner-sharing with trigonal pyramidal TeO3 units to form sheets. The lone-pair of electrons from the TeO3 groups are oriented in opposite directions with respect to one another on each side of the sheets rendering each individual sheet nonpolar. The potassium cations form contacts with nearby tellurite units and axial uranyl oxygen atoms. Crystallographic data (193 K, MoKα, ): triclinic, space group , , , , α=99.642(1)°, β=93.591(1)°, γ=100.506(1)°, , Z=1,R(F)=4.19% for 149 parameters and 2583 reflections with I>2σ(I). 相似文献
65.
66.
Single crystals of a diphosphate NaLuP2O7 have been synthesized by the flux method and characterized by single-crystal X-Ray diffraction. NaLuP2O7 crystallizes in the monoclinic system with P21/n space group with cell parameters: a = 8.9985(8) Å, b = 5.3473(5) Å, c = 12.756(1) Å, β = 103.174° (1), V = 597.67 (9) Å3, Z = 4. Its structure consists of a three-dimensional framework of P2O7 units that are corner-shared by LuO6 octahedra, forming tunnels running parallel to [010] which are occupied by Na atoms. NaLuP2O7 powder was characterized by XRD, SEM, FTIR and Raman spectroscopy. The activation energy of (1.49 eV) obtained by electrical measurements suggests the charge carriers to be the sodium cations. The activation energies obtained from impedance and loss spectra were analyzed in order to explain the mechanism of conduction. The correlation between ionic conductivity of NaLuP2O7 and its crystallographic structure was investigated and the most probable transport pathway model was determined. 相似文献
67.
Fathia Rajah Mohsen Graia Tahar Mhiri 《Phosphorus, sulfur, and silicon and the related elements》2013,188(9):1244-1253
Abstract Sodium copper (II) arsenate Na7Cu4(AsO4)5 has been grown by conventional high-temperature, solid-state methods in molten-salt media. It was characterized by single crystal X-ray diffraction (XRD), thermal analysis (DTA–TGA), scanning electron microscopy (SEM), semiquantitative energy dispersive spectroscopy analysis (EDS), and vibrational spectroscopy. Na7Cu4(AsO4)5 exhibits a three-dimensional framework built up of CuO5, CuO4, and AsO4 polyhedra, with intersecting channels in which the Na+ cations are located. The three-dimensional cohesion of the framework results from Cu–O–As bridges. CuO5 and CuO4 polyhedra are elongated due to the Jahn–Teller effect, whereas AsO4 tetrahedra are almost regular. This new structural model is validated by the charge distribution (CD) analysis. The infrared and Raman spectra confirmed the presence of AsO4 tetrahedra. [Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional tables and figures.] 相似文献
68.
Gloria Subías Joaquín García Javier Blasco Javier Herrero‐Martín M. Concepción Sánchez Julia Orna Luis Morellón 《Journal of synchrotron radiation》2012,19(2):159-173
The pattern of charge modulations and local anisotropies below the Verwey transition has been determined and quantified in high‐quality Fe3O4 single crystals and thin films grown on MgO by using resonant X‐ray scattering at the Fe K‐edge. The energy, polarization and azimuthal angle dependencies of an extensive set of reflections with potential sensitivity to charge or local anisotropy orderings have been analyzed to explore their origins. A charge disproportion on octahedral B sites of 0.20 ± 0.05 e? with [0 0 1] and cubic periodicities has been confirmed, while no significant charge disproportion has been obtained with [0 0 1/2] cubic periodicity. Additional charge modulations in the monoclinic a–b plane are also present. In addition, the occurrence of new forbidden (1, 1, 0) and (0, 0, 2n + 1/2) cubic reflections that arise from the anisotropy of the local structure around different tetrahedral and octahedral Fe atoms is shown. This complex pattern of weak charge modulations and local anisotropies is fully compatible with the low‐temperature crystal structure refined in the non‐polar C2/c space group and disproves any bimodal charge disproportion of the octahedral Fe atoms. 相似文献
69.
Influence of Intermolecular Interactions on Valence Tautomeric Behaviors in Two Polymorphic Dinuclear Cobalt Complexes 下载免费PDF全文
Guo‐Ling Li Dr. Shinji Kanegawa Dr. Zi‐Shuo Yao Dr. Sheng‐Qun Su Shu‐Qi Wu Dr. You‐Gui Huang Dr. Soonchul Kang Prof. Dr. Osamu Sato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17130-17135
Two polymorphic structures have been well determined in a valence tautomeric (VT) dinuclear cobalt complex. These polymorphs showed distinct thermal‐ and photomagnetic behavior, and are thus ideal for studying the “pure” intermolecular factors to VT transitions. In polymorph 1A , the VT cations are arranged head‐to‐waist with their neighbors and exhibit weak π???π interactions, resulting in a gradual and incomplete thermal VT transition. In contrast, the cations in polymorph 1B are arranged head‐to‐tail and exhibit relatively strong π???π interactions, leading to an abrupt and complete thermal VT transition with adjustable hysteresis loop at around room temperature. The VT process for both polymorphs can be induced by light, but the light‐excited state of 1B? 2H2O has a higher thermal relaxation temperature than that of 1A? 3H2O. 相似文献
70.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(11):896-904
Since the discovery of electrochemically active LiFePO4, materials with tunnel and layered structures built up of transition metals and polyanions have become the subject of much research. A new quaternary arsenate, sodium calcium trinickel aluminium triarsenate, NaCa1–x Ni3–2x Al2x (AsO4)3 (x = 0.23), was synthesized using the flux method in air at 1023 K and its crystal structure was determined from single‐crystal X‐ray diffraction (XRD) data. This material was also characterized by qualitative energy‐dispersive X‐ray spectroscopy (EDS) analysis and IR spectroscopy. The crystal structure belongs to the α‐CrPO4 type with the space group Imma . The structure is described as a three‐dimensional framework built up of corner‐edge‐sharing NiO6, (Ni,Al)O6 and AsO4 polyhedra, with channels running along the [100] and [010] directions, in which the sodium and calcium cations are located. The proposed structural model has been validated by bond‐valence‐sum (BVS) and charge‐distribution (CHARDI) tools. The sodium ionic conduction pathways in the anionic framework were investigated by means of the bond‐valence site energy (BVSE) model, which predicted that the studied material will probably be a very poor Na+ ion conductor (bond‐valence activation energy ∼7 eV). 相似文献