Methanol transformations on framework lithium zirconium vanadate phosphates

The catalytic activity of framework phosphates of the general formula LiZr₂(VO₄)_x(PO₄)_3–x with different degrees of phosphorus replacement (x = 0, 0.1, 0.3, 0.4, 0.6, and 0.8) was studied in methanol transformations in an inert atmosphere. It was shown that the ratio between the activity and selectivity of the catalysts in dehydration and dehydrogenation reactions is determined by their vanadium content and the process temperature.     

Synthesis of sodium zirconium phosphates

Zr(O₃PONa)₂ · nH₂O can be prepared as a single crystalline phase by direct precipitation in the presence of HF. This material is a powder. When a single crystal of -HZrP is exchanged with Na⁺, Zr(O₃PONa)₂ · nH₂O is obtained as a powder-like crystal. The zero level Weisenberg photograph shows a monoclinic symmetry; the unit cell (a = 0.900 nm, b = 1.059 nm, c = 2.210 nm and β = 117.12°) contains eight formula units Zr(O₃PONa)₂ · 3H₂O. This is doubled with respect to -HZrP.     

IR study of the structure of rhombohedral zirconium and alkali metal orthophosphates

Zirconium orthophosphates with different alkali cations MZr₂(PO_{4 3}, M₂Zr(PO₄)₂, and M₅Zr(PO₄4)₃, where M is Na, K, Rb, Cs, were synthesized and studied by IR spectroscopy. X-ray diffraction, and ⁴⁰K radiometric analysis. It is confirmed that MZr₂(PO_{4 3} (M = Na, K, Rb, Cs) exist as rhombohedral phases crystallizing as NaZr₂(PO_{4 3}) (NZP) structures. For Na₅Zr(PO_{4 3} it is shown that an NZP phase with a monoclinic superstructure is formed as a result of statistical distribution of Na and Zr in the ZrO₆ octahedm and ordered distribution of sodium atoms in the interstices of the channels. Formation of K₂Zr(PO₄)₂ and K₅Zr(PO₄)₃ phases with NZP structures is shown to be possible. Translated from Zhumal Struktumoi Khimii, Vol. 41, No. 1, pp. 74-79, January-February, 2000.     

Synthesis,structure, and thermal expansion of sodium zirconium arsenate phosphates

Sodium zirconium arsenate phosphates NaZr₂(AsO₄) _x (PO₄)_3?x were synthesized by precipitation technique and studied by X-ray diffraction and IR spectroscopy. In the series of NaZr₂(AsO₄) _x (PO₄)_3?x , continuous substitution solid solutions are formed (0 ≤ x ≤ 3) with the mineral kosnarite structure. The crystal structure of NaZr₂(AsO₄)_1.5(PO₄)_1.5 was refined by full-profile analysis: space group R \(\bar 3\) c, a = 8.9600(4)Å, c = 22.9770(9) Å, V = 1597.5(1) ų, R _wp = 4.55. The thermal expansion of the arsenate-phosphate NaZr₂(AsO₄)_1.5(PO₄)_1.5 and the arsenate NaZr₂(AsO₄)₃ was studied by thermal X-ray diffraction in the temperature range of 20–800°C. The average linear thermal expansion coefficients (α_av = 2.45 × 10^?6 and 3.91 × 10^?6 K^?1, respectively) indicate that these salts are medium expansion compounds.     

Catalytic properties of zirconium phosphate and double phosphates of zirconium and alkali metals with a NaZr2(PO4)3 structure

Zirconium orthophosphate Zr₃(PO₄)₄ and double phosphates of zirconium and alkali metals AZr₂(PO₄)₃ (A = Na, K, Rb, Cs) with a NaZr₂(PO₄)₃ structure were synthesized and characterized by X-ray diffraction and electron microprobe analyses and capillary condensation of nitrogen. The catalytic properties of the phosphates in the dehydration of methanol were studied.     

Synthesis and crystal structure of new alkali metal hydrogen tellurates

New alkali metal hydrogen tellurates have been synthesized, and their structures have been determined by X-ray crystallography. Hydrogen tellurates I–VI contain centrosymmetric binuclear anions [Te₂O₁₀H_4+x ]^(4?x)?, where x=0, 1, 2. Hydrogen tellurates II and VI contain, in addition to the binuclear anion, mononuclear species [TeO₆H₄]^2? and Te(OH)₆, respectively. The CNs of alkali metals vary from 8 to 12. In all structures, the hydrogen atoms (of both the hydroxy groups and water molecules) are involved in hydrogen bonding.     

Synthesis and ion-exchange properties of crystalline titanium and zirconium phosphates

The preparation of novel types of inorganic ion-exchangers, titanium and zirconium phosphates and their ion-exchange properties towards strontium ions, are reported and discussed. Ti(HPO₄)₂·2H₂O is shown to be very stable to hydrolysis and to have high exchange capacity in strongly acid medium. In the case of zirconium phosphate, the titration curves with alkaline earth metal hydroxides are strongly affected by hydrolysis of the exchanger and precipitation of insoluble phosphate. The degree of conversion of the exchanger at which phosphate precipitation begins was found to be 80% for Sr²⁺. The comparison of Ti(HPO₄)₂·2H₂O with the corresponding zirconium phosphate dihydrated phase suggests that the former possesses a lattice structure different from that reported for the monohydrated exchanger.This revised version was published online in November 2005 with corrections to the Cover Date.     

LiNaSe,the first inter alkali metal selenide: Synthesis and structure

LiNaSe was synthesized from lithium carbonate and sodium carbonate at 750 °C in a stream of hydrogen loaded with selenium vapour. The crystal structure was determined from single-crystal diffractometer data. The atomic arrangement corresponds to the lead chloride-type structure. The selenium ions are slightly distorted hexagonal close packed. Lithium and sodium ions occupy tetrahedral and octahedral positions respectively. The cations' displacement from the centre of the surrounding chalcogene polyhedra is believed to be caused by cation-cation repulsion.     

Preparation and structure of alkali metal intercalation compounds

The preparation methods of intercalation compounds fall into four main groups: use of alkali metal solutions in liquid ammonia, organometallic reagents, electrochemical methods, and solid state processes. Each of these will be briefly described and a general comparison of the advantages and disadvantages will be made. Structural problems concern the positions occupied by the guest ions and their mobility from one site to one another in the host structure. The resulting ionic conductivity of the intercalation compounds depends on factors such as the ratio between available and occupied sites in the van der Waals gap, the ionicity of the bonds in the host structure, the site geometry, and the nature of the alkali metal.     

Interaction of rare-earth oxides with binary molten mixtures of zirconium and alkali metal fluorides

Isothermal saturation, inductively coupled plasma mass spectrometry (ICP-MS), and X-ray powder diffraction were used to study solubilities of La₂O₃, Sm₂O₃, and Ho₂O₃ in the eutectic mixtures of LiF-ZrF₄, NaF-ZrF₄, and KF-ZrF₄ systems at temperatures from 873 to 1073 K. The solubilities of rare earth oxides in the molten fluorozirconate systems studied decrease in the increasing order of Ln³⁺ ion radii and in the increasing order of alkali metal cation radii in the binary mixture. The thermodynamic parameters of dissolution calculated for the oxides imply the dominance of a chemical dissolution mechanism, and this implication was supported by X-ray powder diffraction data.     

Oxide layers with titanium and zirconium phosphates

Oxide-phosphate layers 20 to 150 μm thick were obtained on titanium by plasma electrolytic deposition in individual and mixed aqueous electrolytes with polyphosphate complexes of zirconium(IV), barium(II), and copper(II). Formation features, thickness, elemental and phase compositions, and surface morphology of the films are presented. Depending on the electrolyte composition, synthesis conditions, and temperature of annealing in air, some simple and double phosphates of titanium and zirconium are formed, including ZrP₂O₇, NaTi₂(PO₄)₃, BaTi₂(P₂O₇)₂, Zr_0.2Ti_0.8P₂O₇, and CuTi₂(PO₄)₃.     

Synthesis and thermal decomposition of acid alkali metal hexafluoroaluminates

Acid alkali hexafluoroaluminates of K and Rb were prepared by precipitation of alkali fluoride containing H₃AlF₆ solutions with ethanol. Compounds were characterized by X-ray diffraction, IR spectroscopy,¹H-NMR and chemical analysis. The constitution is M^I(H₃O)₂AlF₆. Lattice parameters were determined.Dehydration and thermal decomposition were investigated by thermal analysis (TG, DTG, DTA) on a derivatograph-Q and by high temperature X-ray diffraction. Thermal decomposition is accompanied by liberation of H₂O and HF and a condensation of [AlF₆]^3– octahedra forming layer structures. Stable intermediate products are M^IAlF₄·0.5H₂O and M^IAlF₄. At higher temperatures hydrolysis occurs.

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Zusammenfassung Es wurden saure Kalium- und Rubidiumhexafluoroaluminate durch Fällung aus Alkalifluorid enthaltenden H₃AlF₆-Lösungen mit Ethanol dargestellt. Die erhaltenen Verbindungen wurden chemisch, röntgenographisch, IR- sowie¹H-NMR-spektroskopisch charakterisiert. Die Konstitution der Verbindungen ist M^I(H₃O)₂AlF₆. Die Gitterkonstanten wurden aus Röntgendiffraktionsdaten bestimmt. Entwässerung und thermische Zersetzung wurden mittels Heizguiniertechnik und Thermoanalyse (TG, DTG, DTA) an einem Derivatograph-Q untersucht. Bei der thermischen Zersetzung erfolgt eine HF- und H₂O-Abgabe sowie eine Kondensation von AlF ₆ ^3– -Oktaedern unter Ausbildung von Schichtstrukturen. Als stabile Zwischenprodukte wurden M^IAlF₄·0.5H₂O und M^IAlF₄ nachgewiesen. Bei höheren Temperaturen werden Hydrolysereaktionen beobachtet.

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, H₃AlF₆, . M¹(H₃O)₂AlF₆ , - - . . (, , ) Q- , . [AlF₆]^3– . M¹AlF₄·0.5H₂O M¹AlF₄. .

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Presented at the Microsymposium on Halogen Chemistry held in Budapest, 1987.     

Characterization of modified alumina as adsorbents. Modification of alumina with alkali metal phosphates

Summary Alumina may be considerably modified by impregnating at 100°C in the alkali metal phosphate solution. The available solution for modification was the KOH–K₂HPO₄–AlPO₄ (11.51M) solution or the NaOH–Na₂ HPO₄ (0.81.1 M or 11.5M) solution. The appreciable improvement on chromatograms was obtained by preheating of the alumina, especially above 800°C prior to impregnating A further modification may be made by ignition of the alumina impregnated. The x-ray diffraction studies revealed the phase transformation of the alumina inducing the modification, and the essential factor of the present modification method being the thermal treatment of the alumina at temperatures forming -alumina.     

Crystal structure transformations in ammonium and alkali metal perchlorates

A comparative study of the polymorphic transformations in ammonium and the alkali metal perchlorates has been made using differential thermal analysis. Certain correlations have been attempted between the observed trends in the transformation temperatures and available crystallographic and thermodynamic data. The transformation in the case of sodium perchlorate shows pronounced second-order effects. Considerable hysteresis is observed in the transformations in ammonium, potassium, rubidium and caesium perchlorates. Doping of ammonium perchlorate with ammonium phosphate is seen to result in an upward shift in the transformation temperature and an increase in the thermal hysteresis. Prior mechanical and thermal treatment is also seen to result in a broadening of the hysteresis loops in the case of ammonium and potassium perchlorates. The results are explained in terms of contrapolarization effects and the production of strain in the material as a result of prior treatment.     

Molecular structure and microbiological activity of alkali metal 3,4-dihydroxyphenylacetates

The changes in physical, chemical and biological properties of chemical compounds decide about their biological activity. In this paper the molecular structure of alkali metal 3,4-dihydroxyphenylacetates is studied in comparison to 3,4-dihydroxyphenylacetic acid (3,4-DHPAA) using FT-IR, FT-Raman and UV–Vis spectroscopy as well as density functional theory (DFT) calculations. The B3LYP/6-311++G⁷ method is used to calculate optimized geometrical structures of studied compounds, atomic charges (Mulliken, APT, NBO), dipole moments, energies as well as the wavenumbers and intensities of the bands in vibrational spectra. Theoretical parameters are compared to the experimental data. The relationship between spectroscopic parameters of studied compounds and their biological activity is analyzed. Antioxidant activity is studied using FRAP and DPPH methods. IC₅₀ parameter is also calculated. Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli and Klebsiella oxytoca are used in microbiological analysis of 3,4-DHPAA as well as its sodium and potassium salts.     

Synthesis and alkali metal complexation studies of novel cage-functionalized cryptands

The synthesis of novel cage-functionalized cryptands 1–5 containing adamantane-, 2-oxaadamantane- or noradamantane-moiety [i.e., 1,3-diethyladamantano[2.2.0]cryptand (1), 1,3-diethoxyadamantano[2.2.2]cryptand (2), 1,3-di[(ethyloxy)methyl]adamantano[2.2.2]-cryptand (3), 1,3-di[(ethyloxy)methyl]-2-oxaadamantano[2.2.3]cryptand (4), and 1,2-diethyloxynoradamantano[2.2.2]cryptand (5)] and their alkali metal binding properties are reported. The results obtained by extraction experiments showed that all the cryptands displayed lower extraction capabilities than the parent [2.2.2]cryptand. However, cryptands 1 and 2 showed much higher selectivity toward K⁺ than the reference [2.2.2]cryptand. When the third bridge is enlarged by two additional CH₂-groups as well as by two oxygen atoms, as in cryptands 3 and 4, the complexational abilities for bigger cations (K⁺, Rb⁺ and Cs⁺) are enhanced. Cryptand 5 displayed very good extraction capabilities of all cations, but showed practically no selectivity towards any of the alkali metal cation. The experimental findings are corroborated by calculation studies consisting of force field based conformational search using Monte Carlo method followed by investigation of the stabilities of the complexes of cryptands with Na⁺ and K⁺ metal ions in chloroform by means of quantum chemical calculations at the density functional theory level.     

Comparative study of layered tetravalent metal phosphates containing various first-row divalent metals. Synthesis, crystalline structure

The transition metal forms of α-zirconium-. titanium-, and hafnium phosphates were prepared by ion exchange method. Their structure was investigated by X-ray powder diffraction (XRPD) method. It was found that the transition metal containing phosphates have the same layered structure as the pristine tetravalent metal phosphates, except for the increase of interlayer distance from 7.6 Å to ～9.5 Å. As a result of the incorporation of transition metals in the layers, the c-axis is increased from ～15 Å to ～20 Å (in the case of titanium phosphate to ～25 Å). All other parameters (a, b and β °) are practically unchanged.