Internal Mobility, Phase Transitions, and Ionic Conductivity in Na(NH4)6Zr4F23 and Li(NH4)6Zr4F23

The dynamics of fluoride and ammonium ions in Na(NH₄)₆Zr₄F₂₃ (I) and Li(NH₄)₆Zr₄F₂₃ (II) was studied by ¹H and ¹⁹F NMR in the temperature range 170-440 K. Types of ionic motion were determined, and their activation energies were evaluated. In I, phase transitions were found in the temperature ranges 360-370 and 410-415 K. The experimental values of conductivity of Na(NH₄)₆Zr₄F₂₃ and Li(NH₄)₆Zr₄F₂₃ ( 4 × 10^-3 S/cm at T = 420 K) permit one to attribute these fluorides to the class of superionic conductors.     

Les systemes binaires AlPO4−M3PO4 (M=Li,Na, K)

The liquid-solid phase diagram of the binary systems AlPO₄?M₃PO₄(M=Li, Na, K) have been established. The additional compounds Na₃Al(PO₄)₂, Na₃Al₂(PO₄)₃ and K₃Al₂(PO₄)₃ have been found again. A new compound K₃Al(PO₄)₂ is observed. The melting point of Na₃PO₄ is 1545°C and K₃PO₄ does not melt up to 1700°C.     

Octacoordination of the nitrogen atom in M4NO 4 + systems (M = Li, Na, K)

The electronic and geometric structures of M₄NO ₄ ⁺ compounds (M = Li, Na, K) in classical and nonclassical isomeric forms were studied by the ab initio (MP2(full)/6-311+G**) and density functional theory (B3LYP/6-311+G**) methods. For all M atoms, structurally stable nonclassical isomers were found with octacoordinated nitrogen atoms and tetracoordinated oxygen atoms. For Li₄NO ₄ ⁺ , the classical structure with the tetracoordinated nitrogen atom is energetically more stable, whereas nonclassical structures with the octacoordinated nitrogen center are more stable for Na₄NO ₄ ⁺ and K₄NO ₄ ⁺ .     

Probing Lewis acidity of Y(BH4)3 via its reactions with MBH4 (M = Li, Na, K, NMe4)

High-energy milling of Y(BH(4))(3) (containing LiCl as a by-product, which has not been removed) with MBH(4) (M = Li, Na, K, (CH(3))(4)N) leads to the first two examples of quasi-ternary yttrium borohydrides: KY(BH(4))(4) and (CH(3))(4)NY(BH(4))(4), while no chemical reaction is observed for LiBH(4) and NaBH(4). KY(BH(4))(4) is isostructural to NaSc(BH(4))(4) (Cmcm, a = 8.5157(4) ?, b = 12.4979(6) ?, c = 9.6368(5) ?, V = 1025.62(9) ?(3), Z = 4), while (CH(3))(4)NY(BH(4))(4) crystallises in primitive orthorhombic cell, similarly to KSc(BH(4))(4) (Pnma, a = 15.0290(10) ?, b = 8.5164(6) ?, c = 12.0811(7) ?, V = 1546.29(17) ?(3), Z = 4). The thermal decomposition of hydrogen-rich KY(BH(4))(4) (8.6 wt.% H) involves the formation of an unidentified intermediate at 200 °C and recovery of KBH(4) at higher temperatures; at 410 °C, KCl and YH(2) are observed. The thermal decomposition of (CH(3))(4)NY(BH(4))(4) occurs via two partly overlapping endothermic steps with concomitant emission of H(2) and organic compounds. Heating of a NaBH(4)/Y(BH(4))(3) mixture above 165 °C results in a mixed-cation mixed-anion borohydride, NaY(BH(4))(2)Cl(2), but not NaY(BH(4))(4). The reduced reactivity of Y(BH(4))(3) towards borohydride Lewis bases when compared to hypothetical scandium borohydride can be explained by the lower Lewis acidity of Y(BH(4))(3) than Sc(BH(4))(3).     

MAlH4(M=Li,Na)储氢材料*

氢能是一种新型的清洁能源,有望替代碳经济,而氢的储存是氢能应用的关键。近年来,研究集中在具有储氢容量高和可逆性好等优点的固态储氢材料上。许多新型储氢材料不断出现,其中以MAlH₄(M=Li, Na)为代表的金属复合氢化物体系被认为是最有前景的储氢材料之一。本文综述了MAlH₄(M=Li, Na)作为可逆储氢材料的研究现状,主要从吸放氢反应、储氢性能、反应机理、理论计算和存在的问题等方面进行了讨论,并指出其相关发展趋势。     

(NH4)4M(Zr(Hf))3F17 · 2HF Complexes (M = Li,Na): Synthesis and Physicochemical Properties

Monoclinic crystals of ammonium hydrofluoride fluoro complexes of zirconium and hafnium (NH₄)₄M(Zr(Hf))₃F₁₇ · 2HF (M = Li, Na) are synthesized and studied. Their unit cell parameters are determined. IR spectra of the synthesized compounds are measured in the range of 350–4000 cm^–1.     

Die Systeme des Typs MCl/AlCl3/SO2 (M = Li,Na, K,NH4)

The MCl/AlCl₃/SO₂ Systems (M = Li, Na, K, NH₄) Phase diagrams of the ternary systems of the type MCl/AlCl₃/SO₂ were determined by measurement of SO₂ pressure, solubilities, and by thermal analysis. The complete phase diagram in the range from ?30 to +50°C is given for the case M = Na, partial diagrams for M = Li, K, NH₄. There exist solid compounds of the type MAlCl₄ · nSO₂ (M = Li, Na; n = 1.5 and 3) (M = K; n = 1.5 and 5) (M = NH₄; n = 5). Liquid phases can be obtained at room temperature and atmospheric pressure in the NaCl or LiCl containing systems.     

Calorimetric investigations of the MBr−NdBr3 melts (M=Li,Na, K,Cs)

Present work is a part of thermodynamic research program on the MX?LnX₃ system (M=alkali metal,X=Cl, Br andLn=lanthanide). Molar enthalpies of mixing in the LiBr?NdBr₃, NaBr?NdBr₃ and KBr?NdBr₃ liquid binary systems have been determined at temperature 1063 K by direct calorimetry in the whole range of composition. Investigated systems are generally characterized by negative enthalpies of mixing with minimum atX _NdBr3≈0.3–0.4. These enthalpies decrease with decrease of ionic radii of alkali metals. Molar enthalpies of solid-solid and solid-liquid phase transitions of K₃NdBr₆ and Cs₃NdBr₆ have been also determined by differential scanning calorimetry (DSC). K₃NdBr₆ is formed at 689 K from KBr and K₂NdBr₅ with enthalpy of 44.0 kJ·mol^?1 whereas Cs₃NdBr₆ is stable at ambient temperature and undergoes phase transition in the solid state at 731 K with enthalpy of 8.8 kJ·mol^?1. Enthalpies of melting have been also determined.     

X-ray photoelectron spectroscopy as detection tool for coordinated or uncoordinated fluorine atoms demonstrated on fluoride systems NaF,K2TaF7, K3TaF8, K2ZrF6, Na7Zr6F31 and K3ZrF7

While systems K₃TaF₈ and K₃ZrF₇ were prepared by modified molten salt method modified wet pathway was used for reproducible preparation of Na₇Zr₆F₃₁. Its congruently melting character was demonstrated on simultaneous TG/DSC measurements and XRD patterns. X-ray photoelectron spectroscopy was applied for identification of differently bonded fluorine atoms in series of compounds NaF, K₂TaF₇, K₃TaF₈, K₂ZrF₆, Na₇Zr₆F₃₁ and K₃ZrF₇. Three different types of fluorine atoms were described qualitatively and quantitatively. Uncoordinated fluorine atoms (F⁻) provide signals at lowest binding energies, followed by signals from terminally coordinated fluorine atoms (M–F) and then bridging fluorine atoms (M–F–M) at highest energy. Based on XPS F 1s signals assigned to fluorine atoms in compounds with correctly determined structure it was suggested that fluorine atoms in K₃ZrF₇ have partially bridging character.     

Thermal Analysis of Pseudoternary Systems Me4P2O7-WO3-MeCl (Me = Na,K)

Thermal analysis of the pseudoternary systems Na₄P₂O₇-WO₃-NaCl and K₄P₂O₇-WO₃-KCl was performed, and the crystallization fields were revealed of sodium and potassium pyrophosphates, incongruently melting compounds Na₄P₂O₇·3WO₃ and K₄P₂O₇·3WO₃, and of products formed by reactions of WO₃ with NaCl and KCl. Low-melting compositions were revealed, which are of interest for preparing Na(K)-W oxide bronzes.     

Les systèmes MFTlF3 (M = Li,Na, K)

A large number of new phases have been prepared and characterized in the MFTlF₃ system: Na₃TlF₆ isostructural with cryolite, Na₃Tl₂F₉, Na_xTl_1−xF_3−2x (0.425 ? x ? 0.565 at 500°C) and Na₅Tl₉F₃₂ related to the fluorite type, K₃TlF₆ with a structure similar to that of (NH₄)₃FeF₆, K₅Tl₃F₁₄ with the chiolite structure, Na_yTl_1−yF_3−2y (0.12 ? y ? 0.14 at 500°C) and K₂Tl₇F₂₃ affiliated to α-UO₃, KTlF₄, and KTl₂F₇.     

Phase formation in the systems TiOCl2-H3PO4-MF(HF)-H2O (M = K, Rb, Cs)

From solutions containing 2–17 wt % TiO₂ at the molar ratios M/Ti = 1–4, F/Ti = 2–4, and PO ₄ ^3? /Ti = 0.5–10 under mild conditions, fluoro- and oxo(hydroxo) fluorophosphate titanates were isolated: crystalline M₂TiF₆ (M = K, Rb, Cs) and K₂Ti₂O_2.5F₂PO₄ · 2H₂O, and amorphous K₃Ti₄O(OH)F₇(PO₄)₃ · 5H₂O, Cs₂Ti₃O₂F₇PO₄ · 6H₂O, and CsTi₃O₃F₄PO₄ · 3H₂O. In a mixture with M₂TiF₆ and KCl, phosphate-ion-containing crystalline phases of unidentified composition were detected. The phases were studied by elemental, crystal-optical, X-ray powder diffraction, thermal, IR spectroscopic, and electron microscopic analyses. Annealing fluorophosphate titanates gives a mixture of MTiOPO₄ and TiO₂. All the mentioned alkali metal fluorophosphates contain the tetrahedral ion PO ₄ ^3? and titanium polyhedra with bonds Ti-F and Ti-O; some of them also contain bridging oxygen connecting titanium atoms: Ti-O-Ti; i.e., these substances are polymeric.     

Nuclear quadrupole resonance in MSbClF3 compounds (M=Na,K, Cs,NH4)

Conclusion A study of the temperature dependence of the¹²³Sb NQR parameters for MSbClF₃ complexes (M=K, Cs, NH₄) at from 77 to 390K shows temperature ranges with anomalous change in the electric field gradient asymmetry parameter for the antimony atoms.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1136–1139, May, 1987.The authors express their gratitude to G. K. Semin for a useful discussion of this work.     

Phase formation in the Re-Se-Br-MBr systems (M = Li, Na, K, Rb, Cs)

Phase formation in the Re-Se-Br-MBr systems (M = K, Rb, Cs) was studied by NMR spectroscopy and powder X-ray diffraction. The reactions taking place in alkali metal halide melts were found to give, among the series of cluster anions [{Re₆Se_{8 − n} Br _n }Br₆]^{(4 − n)}− (0 ≤ n≤ 4), polymeric complexes Re₆Se₈Br ₂ and M₂Re₆Se₈Br₄ (M = Cs, Rb) and salts containing cluster anions [Re₆Se₆Br₈]²⁻ and [Re₆Se₇Br₇]³⁻ as the major products. The effect of the alkali metal cation on the product composition and ratio was established. Original Russian Text ? S.S. Yarovoi, Yu.V. Mironov, S.V. Tkachev, V.E. Fyodorov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 2, pp. 344–349.     

121Sb Mössbauer spectra of alkali metal antimonides M3Sb (M3 = Na3, K3, Na2K, Rb3)

¹²¹Sb Mössbauer spectra for M₃Sb (M₃ = Na₃, K₃, Na₂K, Rb₃) were measured at 12 K. The values of isomer shift (d) and quadrupole coupling constant suggest that the valence state of antimony in M₃Sb is –3. The d values increase in the order Rb₃Sb<K₃Sb<Na₃Sb<Na₂KSb. The differences in d values are discussed by examining M–Sb distances and bond valence for M–Sb interactions. Some covalent interactions between alkali metal atoms and antimony atom are suggested.     

New examples of metalloaromatic Al-clusters: (Al4M4)Fe(CO)3 (M = Li, Na and K) and (Al4M4)2Ni: rationalization for possible synthesis

Ab initio calculations reveal that all-metal antiaromatic molecules like Al4M4 (M = Li, Na and K) can be stabilized in half sandwich (Al4M4)Fe(CO)3 and full sandwich (Al4M4)2Ni complexes. The formation of the full sandwich complex [(Al4M4)2Ni] from its organometallic precursor depends on the stability of the organic-inorganic hybrid (C4H4)Ni(Al4Li4).     

Structure determination and relative properties of novel cubic borates MM'4(BO3)3 (M = Li, M' = Sr; M = Na, M' = Sr, Ba)

A series of novel borates, MM'4(BO3)3 (M = Li, M' = Sr; M = Na, M' = Sr, Ba), have been successfully synthesized by standard solid-state reaction. The crystal structures have been determined from powder X-ray diffraction data. They crystallize in the cubic space group Iad with large lattice parameters: a = 14.95066(5) A for LiSr4(BO3)3, a = 15.14629(6) A for NaSr4(BO3)3, and a = 15.80719(8) A for NaBa4(BO3)3. The structure was built up from 64 small cubic grids, in which the M' atoms took up the corner angle and the BO3 triangles or MO6 cubic octahedra filled in the interspaces. The isolated [BO3]3- anionic groups are perpendicular to each other, distributed along three 100 directions. The anisotropic polarizations were counteracting, forming an isotropic crystal. Sr and Ba atoms were found to be completely soluble in the solid solution NaSr(4-)xBax(BO3)3 (0 < or = x < or = 4). The photoluminescence of samples doped with the ions Eu2+ and Eu3+ was studied, and effective yellow and red emission was detected, respectively. The results are consistent with the crystallographic study. The DTA and TGA curves of them show that they are chemically stable and congruent melting compounds.