Co-cation Conduction in Solid Solutions (K1 – xRbx)4P2O7–M2P2O7(M = Ca,Sr, Cd,Ba): Dependence on the Nature and Concentration of Cations M2+

Solid solutions of the structure -K₄P₂O₇, which have the composition (K_{1 – x} Rb _x )_3.8M_0.1P₂O₇(M = Ca, Sr, Cd, Ba) and (K_{1 – x} Rb _x )_{4 – 2y} Ca _y P₂O₇(y= 0.025–0.20), are synthesized. The solutions' electroconductivity is studied in the temperature range 400–600°C. The concentration dependences of the conductivity and the activation energy for conduction have extremums at x 0.6, which points to the polyalkaline effect. The effect increases with decreasing radius of cation M²⁺and with increasing concentration of calcium cations, which is explained by an increased energy nonequivalence of positions in the cation sublattice accessible to alkali ions.     

Electroconductivity of Solid Solutions Cs3–2x M x PO4 (M = Ba, Sr, Ca, Mg)

Solid solutions Cs_{3 – 2x} M _x PO₄ (M = Ba, Sr, Ca, Mg) are synthesized and their thermal behavior and electroconductivity are examined. Adding elements of Subgroup IIA of the periodic table into cesium orthophosphate shifts the phase transition, which occurs in pure Cs₃PO₄ at 450–620°, towards lower temperatures and raises the cesium cation conductivity at low temperatures. The electroconductivity of a high-temperature modification of Cs₃PO₄ is weakly dependent on the presence and concentration of such additives, which points to structural disordering of the cesium sublattice.     

Electroconductivity of Solid Electrolytes in the Systems K3–2x M x PO4 (M = Ca, Sr, Ba)

Solid electrolytes K_{3 – 2x} M _x PO₄ (M = Ca, Sr, Ba) are synthesized and the temperature and concentration dependences of their electroconductivity are studied. Adding calcium and strontium stabilizes the high-temperature -form of K₃PO₄ at room temperature, while barium-containing solid electrolytes undergo an eutectoid decomposition below 430°C. Maximum electroconductivity is exhibited by K_{3 – 2x} Sr _x PO₄ (7.1 × 10^–3 and 1.25 × 10^–1 S cm^–1 at 300 and 700°C).     

Electroconduction of Solid Solutions Na3 – 2x M x PO4(M = Cd, Pb)

In the sodium-orthophosphate-based solid solutions in Na_{3 – 2x} M _x PO₄ systems (M = Cd, Pb), the electroconduction is maximum near the upper concentration boundaries of the single-phase regions: x 0.4 for M = Cd and x 0.25 for M = Pb. The conductivity values at 300°C are 6.25 × 10^–3 and 2.5 × 10^–3 S/cm, respectively. The conduction of synthesized solid electrolytes has a co-cation nature. Their electric characteristics, inferior to those of the Na₃PO₄-based solid solutions obtained via heterovalent substitutions of another type, may be a manifestation of an effect similar to the polyalkali effect.     

Gas-Phase Reactions of hydrated alkaline earth metal ions, M2+(H2O) n (M = Mg, Ca, Sr, Ba and n = 4–7), with benzene

Gas-phase reactions of hydrated divalent alkaline earth metal ions and benzene were investigated by electrospray ionization Fourier-transform mass spectrometry. Rate constants for solvent-exchange reactions were determined as a function of hydration extent for Mg2+, Ca2+, Sr2+, and Ba2+ clusters containing four to seven water molecules each. All of the strontium and barium clusters react quickly with benzene. Barium reacts slightly faster than the corresponding strontium cluster with the same number of water molecules attached. For calcium, clusters with four and five water molecules react quickly, whereas those with six and seven water molecules do not. Magnesium with four water molecules reacts quickly, but not when five through seven water molecules are attached. The slow reactivity observed for some of these clusters indicates that the cation-pi interaction between the metal ion and benzene is partially screened by the surrounding water molecules. The reactivity of magnesium with seven water molecules is intermediate that of the hexa- and pentahydrate and the tetrahydrate. This result is consistent with the seventh water molecule being in the outer shell and much more weakly bound. The unusual trend in reactivity observed for magnesium may be due to the presence of mixed shell structures observed previously. These results are the first to provide information about the relative importance of cation-pi interactions in divalent metal ions as a function of metal hydration extent. Such studies should also provide a model and some insight into the relative binding affinities of divalent metal ions to aromatic residues on peptides and proteins.     

Protonic and Oxygen Conduction of Perovskites ATi0.95M0.05O3 - α (A = Ca,Sr, Ba; M = Mg,Sc) in Humid Air

Measurements of the total conduction (450-1030°C) and transport numbers for ions and protons (450-850°C) of titanates ATi_0.95M_0.05O_{3 -} (A = Ca, Sr, Ba; M = Mg, Sc) in humid air are performed. Partial conductions (ionic, protonic, oxygen, hole) and their effective energies of activation are determined. The results are discussed within a model of separate transport of proton and oxygen ion.     

MO-RE2O3-B2O3(M=Mg,Ca,Sr,Ba;RE=La,Eu,Gd)玻璃的发光性质

在空气中采用高温固相反应方法合成的17MO－（8-x-y)-75B2O3-xGd2O3(MLBEG,M-Mg,Ca,Sr,Ba)玻璃，在紫外光（λex=350nm)激发下发射蓝光和红光，在绿色光（λex=532nm)激发下发射红光，电子自旋共振谱研究表明玻璃体系中有Eu^2 离子存在，蓝色区的宽带发射是Eu^2 离子的5d-4f跃迁发射：红色区的窄带发射是Eu^3 离子的5Do-7FJ(J=1,2,3,4)跃迁发射，发现玻璃中的碱土金属离子对Eu^3 /Eu^2 离子的比例有很大影响，选择不同的碱土金属离子可以调节玻璃蓝色光和红色光的相对发射强度，MLBEG玻璃的发光性质可用于转换太阳能，增强植物的光合作用。     

MF_2-xMgF_2(M=Ca,Sr,Ba)体系中Eu~(2+)离子的光谱特性

BaMgF_4不仅是良好的压电材料,而且也是Eu~(2+)离子激活磷光体的良好基质。MF_(2-x)MgF_2(M=Ca,Sr,Ba;x=1.0,2.0)中Eu~(2+)离子的荧光发射波长随M~(2+)离子半径增大向短波方向移动;并观察到了 BaF_2-_xMgF~2(x=1.5～2.5)体系中Eu~(2+)离子的f→f跃迁尖峰发射(360nm),当x=2.0时,其发射强度最大。     

Eu2+在M3La3(BO3)4(M=Ca,Sr,Ba)中的发光性质

本文研究了Eu²⁺离子在M_yAl_xBO_y+3/2(1+x)(M=Ca,Sr,Ba)基质中的发光性质及磷和卤素对发光的影响。 采用以H₂和N₂混合气体为还原气氛在高温下进行固相反应的方法合成了一系列磷光体。发现,在CaAl_xBO_2.5+3/2x基质中,当X在0.5～2的范围内时及在Sr_yAl₂BO_{4 6+}基质中,当y在2～6的范围时掺入的Eu³⁺不能被H₂还原为Eu²⁺。其他Eu²⁺激活的磷光体一般都产生f～d跃迁的宽带发射,发射峰的波长随着基质组成的不同可在400～600nm的区间的变化。     

M(CN)(2) Species (M = Be, Mg, Ca, Sr, Ba): Cyanides, Nitriles, or Neither?

The "cyanide" salts of the group 2 (alkaline earth) metals exhibit remarkable structural variations: CN(-) binds to the metals via the carbon, via the nitrogen, and via bridged arrangements. The most stable geometries of the beryllium and the magnesium salts are linear (CNBeNC and NCMgCN, respectively), but CaC(2)N(2), SrC(2)N(2), and BaC(2)N(2) prefer twisted, bridged structures. However, several stationary points of the bridged complexes are close in energy, and considerable fluxionality is to be expected. These theoretical predictions (MP4SDTQ/6-311+G(2d)//MP2(fu)/6-31+G, Ca, Sr, Ba: 5s5p3d1f//5s5p3d basis sets and 10 valence electron pseudopotentials) invite experimental verification.     

Conduction and Transport Numbers in Metacomposites MeWO<Subscript>4</Subscript> ⋅ WO<Subscript>3</Subscript> (Me = Ca,Sr, Ba)

The conduction and transport numbers of charge carriers for composites in the systems MeWO₄-WO₃ (Me = Ca, Sr, Ba) are studied as a function of the temperature and the activity of oxygen in a gas phase. The transport numbers are determined by an emf method and are estimated from dependences of conductance on the activity of oxygen in a gas phase. The deficiencies of the given procedure as applied to investigation of properties of composite phases are analyzed. The materials under study are classified with a class of metacomposites. The concentration intervals of the ionic, mixed, and electronic conductions are determined. The conduction of composites of compositions (100 − x)MeWO₄ ⋅ xWO₃ is predominantly ionic at x ≤ 10 (Me = Ca), x ≤ 60 (Me = Sr), and x ≤ 45 (Me = Ba). The obtained data are explained in the framework of a model that represents a composite as a distributed matrix system where a film of surface phase MeW-s with a high mobility of oxygen ions plays the role of a connected matrix. It is presumed that the surface phase MeW-s possesses double-sided surface activity (α _MeW-s ≤ ) and a higher mobility with respect to MeWO₄ and WO₃. The discovered anomalies of dependences (T) and partial dependences , σ_el(T) are explained by a change in the stoichiometry, morphology, and the degree of connectedness of surface phase MeW-s caused by with a change in the temperature and composition of composites.__________Translated from Elektrokhimiya, Vol. 41, No. 6, 2005, pp. 680–693.Original Russian Text Copyright © 2005 by Neiman, Pestereva, Sharafutdinov, Kostikov.Published on the basis of a report delivered at the VII Meeting on Fundamental Problems in Solid-State Ionics (Chernogolovka-2004).     

Coefficients of Linear Thermal Expansion of Solid Electrolytes with Co-cation Conduction Based on γ-K4P2O7, γ-KFeO2, and γ-LiAlO2 Structures

Linear thermal expansion coefficients (K) for co-cation solid electrolytes of three types are measured. The electrolytes include solid solutions (K_{1 – x} Rb _x )_3.8Me_0.1P₂O₇ (Me = Ca, Ba) with the structure of -K₄P₂O₇ (I); fcc-solid solutions (A_{1 – x} A" _x )MO₂–EO₂ (A, A" = K, Rb, Cs; M = Al, Ga, Fe; E = Si, Ge, Ti) of -KFeO₂ type (II); and tetragonal solid solutions 0.8(Li_{1 – x} Na _x AlO₂) · 0.2TiO₂ with the LiAlO₂ structure (III). Dependences of K on the ratio of alkali cation amounts in I and II have a maximum, i.e. the polyalkali effect (PAE) of K is observed, while in III this dependence is practically linear (PAE of K is absent). The correlation is found between PAE of K and the electroconductivity of the electrolytes.     

MCl2-TiO2-SnO2 (M=Mg, Ca, Sr, Ba) 催化剂甲烷氧化偶联反应性能的研究

选用不同的碱土金属氯化物为原料,采用共研磨的方法制备出了具有不同表面碱性的MCl2-TiO2-SnO2(M=Mg,Ca,Sr,Ba)催化剂,并考察了催化剂的甲烷氧化偶联反应性能.通过N2吸脱附(BET)、X-射线衍射(XRD)、X-射线光电子能谱(XPS)和CO2程序升温脱附(CO2-TPD)等技术对催化剂进行了表征.结果表明,随碱土金属元素的不同,催化剂呈现出了强弱不同的碱性吸附位.催化剂表面的碱性对活化甲烷具有促进作用,同时也带来乙烯深度氧化副反应的发生.碱量越大的弱碱性吸附位对甲烷的活化越有利,而强碱性吸附位则能导致催化剂活性降低,甚至是催化剂失活.乙烯的选择性与催化剂表面晶格氧的相对浓度密切相关.表面晶格氧的相对浓度较高的催化剂,其乙烯选择性也较大.     

MMgF4(M=Ca,Sr, Ba)体系中Eu和Tb的电荷迁移

于不同气流中, 合成了MMgF4:xEu,yTb复合氟化物磷光体。该体系中Eu^3^+和Eu^2^+共存。Tb的存在影响Eu的价态存在形式。ESR测试表明, 随Tb的掺入浓度增加, Eu^2^+的浓度呈规律性变化。随Eu的掺入, 样品的XPS谱中出现了四价铽的Tb3d5/2特征伴峰。认为Eu^3^+和Tb^3^+之间存在电荷迁移平衡。即Eu^3^++Tb^3^+=Eu^2^++Tb^4^+。通过半定量手段研究了SrMgF4中这一衡的平衡常数。     

Solid electrolytes with potassium cation conductivity in K1−2x M x AlO2 (M = Ba, Pb) systems

New solid electrolytes with high potassium cationic conductivity based on potassium monoaluminate were synthesized and studied in the K_1?2x Ba _x AlO₂ and K_1?2x Pb _x AlO₂ systems. A partial substitution of potassium cations with double charged positive cations results in a considerable increase in the conductivity of KAlO₂ in the whole studied range of temperatures. The electric characteristics are somewhat higher in the bariumcontaining system, which is in all probability connected with the effect of the size factor: the size of the Ba²⁺ ion is higher than that of Pb²⁺, which must correlate with the increase of the effective dimensions of the migration channels in the electrolyte structure. The main cause of the conductivity increase at the introduction of the studied additives is the formation of potassium vacancies at the substitution of 2K⁺ → Ba²⁺(Pb²⁺) + V′_K.     

Magnetic behaviour of the MTbF6 fluoroterbates (M=Cd,Ca, Sr, (α/β)-Ba)

Neutron powder diffraction has been performed on the MTbF₆ fluorides (M=Cd, Ca, Sr, (α/β)-Ba). Four of these fluorides (Cd, Ca, Sr, β-Ba) are built of a (pseudo-) tetragonal packing of [TbF₆]^2? chains and only differs by the chains relative orientations. Thus this series represents a valuable opportunity to evaluate the Tb⁴⁺-Tb⁴⁺ magnetic interactions. All the compounds displayed antiferromagnetic order (T_N=2.70 K (Cd), 2.15 K (Ca), 2.60 K (Sr), 2.10 K (β-Ba)), except for the α form of BaTbF₆. The crystal structure of this latter fluoroterbate has also been investigated by means of high-resolution neutron powder diffraction. From Neutron Powder Diffraction data, CdTbF₆ and β-BaTbF₆ magnetic structures were determined, together with the metamagnetic behaviour of β-BaTbF₆ as a function of an external magnetic field. A tentative phase diagram is then given for β-BaTbF₆. Advantage was taken of the polymorphism of the BaTbF₆ fluoroterbate to analyse, on the basis of topological parameters such as bond distances and angles, the magnetic behaviour of its α and β forms. It was shown that superexchange interactions are present in β-BaTbF₆, and that these interactions may also rule the magnetic behaviour of the other MTbF₆ (M=Ca, Sr, Cd) tetravalent terbium fluorides.     

Potassium Cationic Conduction in K3 – xP1 – xExO4 (E = S,Cr, Mo,W)

Solid solutions of cubic structure based on K₃PO₄are synthesized in the systems K_{3 – x} P_{1 – x} E _x O₄(E = S, Cr, Mo, W). Approximate boundaries of single-phase regions and the temperature and concentration dependences of electroconductivity are studied. The transport numbers, measured by a modified Tubandt method, confirm a potassium cationic character of conduction. Electric parameters of the electrolytes are compared with those of sodium and rubidium conducting solid solutions in similar systems. Factors that affect transport properties of synthesized phases are discussed.     

Vibrational spectra of pentafluoroperoxo metallates,K2M(O2)F5·H2O (M = Nb,Ta)

The i.r. (4000-50 cm⁻¹) and laser Raman spectra (4000-50 cm⁻¹) of potassium pentafluoroperoxo niobate monohydrate and potassium pentafluoroperoxo tantalate monohydrate have been investigated. The observed spectra have been analysed on the basis of spectral comparison with related compounds and of the normal vibration calculations employing modified Urey-Bradley force functions. While some coupling has been observed for the niobate, the vibrations of the tantalate are nearly localized.     

Ca2.9M0.1Co4O9 (M=Ag,La, Ba)复合氧化物体系的制备及电输运性能

采用柠檬酸溶胶-凝胶结合放电等离子烧结方法制备了p型Ca位掺杂的Ca2.9M0.1Co4O9(M=Ag, La, Ba)复合氧化物块体试样, 对其进行X 射线衍射(XRD)分析, 表明产物为单一物相, Ca位掺杂原子可以改变Ca2.9Co4O9多晶体的取向度, 掺杂试样取向度随着掺杂原子电负性的降低而提高|对其进行扫描电子显微镜(SEM)分析结果表明, 试样呈层状结构, 且层状结构随掺杂原子电负性降低而逐渐明显; 电性能分析结果表明, 测试温度范围内掺杂试样各温度点的电阻率随着掺杂原子电负性的降低而升高, 所有试样的载流子传输层未受影响, 导电机理未发生变化. 其中掺杂电负性最高的Ag原子的烧结体保持最低取向度的同时具有最低的电阻率, 在973 K时达6.87 mΩ·cm, 而掺杂电负性最低的Ba原子的烧结体具有高的取向度的同时具有较高的电阻率, 在973 K时达8.22 mΩ·cm.