Electroconductance of single-crystal Li2 + x Fe 2 − 2x 2+ Fe x 3+ (MoO4)3 (x = 0.22)

Electrophysical properties of single-crystal Li_{2 + x} Fe _{2 ? 2x} ²⁺ Fe _x ³⁺ (MoO₄)₃ (x = 0.22) are studied at 25–400°C. It is found that the conduction is of electronic nature and the conductivity equals 5 × 10^-2 S/cm at 300°C. The activation energy for the electron transport is 0.23 eV. The conductance in molybdate Li_2.22Fe _1.56 ²⁺ Fe _0.22 ³⁺ (MoO₄)₃ is markedly anisotropic.     

Phosphates M 0.5(1 + x) 2+ Cr x Ti2 − x (PO4)3: Synthesis, structure, and catalytic properties

Complex phosphates of titanium, chromium, and metals(2+) of the general formula M_{0.5(1 + x} )Cr _x Ti_{2 ? x} (PO₄)₃ (M = Mg, Ca, Mn, Ni, Sr, Ba, and Pb) were synthesized. Their phase formation was studied by means of X-ray powder diffraction, electron probe microanalysis, differential thermal analysis, and IR spectroscopy. Individual phases and solid solutions crystallizing in kosnarite and langbeinite structure types were identified; their crystallographic parameters were calculated. The catalytic properties of phosphates Ca_{0.5(1 + x} )Cr _x Ti_{2 ? x} (PO₄)₃ in methanol conversion were studied.     

Formation of (C x H2x+1)4NBr·nH2O (x = 1–3) hydrate

The phase diagram of the binary system tetramethylammonium bromide-water was studied by the differential thermal analysis. In the stable region two phases, ice and the salt itself, were detected, and in the metastable region, three tetramethylammonium bromide hydrates (bromide-water, 1 : 4, mp 68.8°C, 1 : 5, mp 36.0°C, 1 : 7.5, mp ?19.5°C) were found. Formation of (C _x H_2x+1)₄NBr·nH₂O (x = 1–3, n = 4, 5, 7.5) hydrates was revealed.     

水热法制备富锂型Li_(2+4x)Mn_(0.6+2x)Ni_(0.6-6x)Cr_(0.8)O_4及其结构与电化学特性

采用水热法制备了系列富锂尖晶石型正极材料Li2+4xMn0.6+2xNi0.6-6xCr0.8O4(x=1/30,1/20,1/15,1/12),通过X射线衍射(XRD)、电感耦合等离子体-原子发射光谱(ICP-AES)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FTIR)、拉曼光谱、循环伏安(CV)和充放电测试等手段对其结构及电化学性能进行表征.结果表明,所制备的系列材料为富锂型高电压尖晶石结构正极材料,该系列样品在4.7 V左右有放电平台.x=1/15和x=1/12时,样品中的Cr为+3价,没有观测到Cr6+.随着x值的增大,样品中Li离子与过渡金属离子的混排减小,样品的充放电比容量逐渐增大,且2.7 V处的放电平台容量也增加.当x=1/12时,样品具有较好的充放电比容量和倍率特性,首次放电比容量为107.3 mA·h/g,20次循环后容量保持率为84.9%.     

High-pressure synthesis and local structure of corundum-type In(2-2x)Zn(x)Sn(x)O(3) (x ≤ 0.7)

The corundum-type In(2-2x)Zn(x)Sn(x)O(3) solid solution (cor-ZITO, x ≤ 0.7) was synthesized at 1000 °C under a high pressure of 70 kbar. cor-ZITO is a high-pressure polymorph of the transparent conducting oxide bixbyite-In(2-2x)Zn(x)Sn(x)O(3) (x ≤ 0.4). Analysis of the extended X-ray absorption fine structure suggests that significant face-sharing of Zn and Sn octahedra occurs, as expected for the corundum structure type. In contrast to the ideal corundum structure, however, Zn and Sn are displaced and form oxygen bonds with lengths that are similar to those observed in high-pressure ZnSnO(3). Powder X-ray diffraction patterns of cor-ZITO showed the expected unit cell contraction with increased cosubstitution, but no evidence for ilmenite-type ordering of the substituted Zn and Sn. A qualitative second harmonic generation measurement, for the solid solution x = 0.6 and using 1064 nm radiation, showed that Zn and Sn adopt a polar LiNbO(3)-type arrangement.     

喷雾干燥法制备Li_(1.2)Mn_(0.4+x)Ni_xCr_(0.4-2x)O_2及其结构与电化学特征

利用喷雾干燥法合成了富锂三元正极材料Li1.2Mn0.4+xNixCr0.4-2xO2(x=0,0.05,0.10,0.15,0.20,以下简称为SD1~SD5),并利用XRD,XPS,ICP,TEM,SEM等手段对材料进行结构,元素价态,形貌及电化学性能等方面的表征。SD1~SD5系列样品都具有层状结构,其所含的Cr元素为Cr6+和Cr3+共存,而Ni元素价态为+2.5价,Mn元素为+4价。SD1~SD4样品中由于存在非晶态的Li2CrO4,导致样品表现出强烈的吸湿性。这个问题可通过水洗处理来解决,且水洗处理对于改善该系列材料的电化学性能有明显的效果。SD1~SD5系列样品中,SD1与SD4样品电化学性能较好,以20 mA.g-1的放电电流密度,在4.8~2.0 V电压区间内,首次放电比容量分别为247和220 mA.h.g-1,经过20次充放电循环后,容量保持率分别为73%和78%。高温条件下SD1和SD4样品的首次放电比容量分别增大为256和237 mA.h.g-1,经过20次充放电循环后容量保持率分别为83%和99%。将充放电电压扩展为5.0~2.0 V时,SD4样品首次放电比容量可以达到307 mA.h.g-1。     

Structural and electrical properties of sol–gel grown (1 − x) (ZnO) + (x) (SnO2) (x = 0, 0.25, 0.5) nanocomposites

Journal of Sol-Gel Science and Technology - Semiconducting oxide nanocomposites of ZnO/SnO2 with different weight ratio, i.e. (i) ZnO:SnO2?=?100:0 (ZnO0), (ii)...     

Anion Transport in Superionic Conductors Na0.5 – x R0.5 + x F2 + 2x (R Are Cations of Rare-Earth Elements) at Elevated Temperatures

Anion conduction in solid solutions Na_{0.5 – x} R_{0.5 + x} F_{2 + 2x} (R = Dy; Ho; Tm; Y; combinations Y_0.9Nd_0.1, Y_0.5Yb_0.5, Lu_0.998Ho_0.002, Lu_0.9Ho_0.1, Lu_0.9Nd_0.1) with a fluorite structure is studied at 251–1073 K. The ion transport mechanism alters at T _c 723–773 K. Below T _c the mechanism involves migration of interstitial fluorine atoms and depends mainly on the defect-containing (clustered) structure of the solid solutions. Above T _c the mechanism probably involves the dissociation of interstitial fluorine atoms from structural clusters, and the anion conductivity reaches 1 S cm^–1. The fluorite solid solution in the Na_0.4Ho_0.6F_2.2 crystals partly decomposes, yielding NaHoF₄ compounds with a gagarinite (NaCaYF₆) structure.     

Layered ionic liquid-crystalline organisations built from nano-capsules [Mo132O312S60(SO4)x(H2O)132−2x](12 + 2x)− and DODA+ cations

Two dimethyldioctadecylammonium (DODA⁺) salts of a new keplerate with the general formula [Mo₁₃₂O₃₁₂S₆₀(SO₄)_x(H₂O)_132–2x]^{(12 + 2x)?} and abbreviated DODA_n?Mo₁₃₂S₆₀ (n = 44, 56) were synthesised and characterised. Both clusters were fully characterised by the combination of Polarised Optical Microscopy, Differential Scanning Calorimetry and Small-angle X-Ray Diffraction showing self-organisation in lamellar (L) liquid crystalline phases. We demonstrated that the lamellar periodicity h of the mesophases can be controlled with the number of DODA⁺ associated to the clusters. Finally, these new results were compared to those gained from a previously published analogue, the fully oxo keplerate noted DODA₃₆?Mo₁₃₂ that also self-organise with temperature, but in a slightly more structured lamellar liquid crystalline phase.     

Glycolate Ti1 − x Fe x (OCH2CH2O)2 − x/2 as a precursor for the preparation of quasi-one-dimensional (1D) solid solutions Ti1 − x Fe x O2 − 2x/2 (0 ≤ x ≤ 0.1)

Quasi-one-dimensional (1D) solid solutions Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} (0 < x ≤ 0.1) with the structure of anatase were prepared by heating the glycolate Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} in an atmosphere of air at a temperature of >450°C. The conditions of formation and the properties of the new glycolate Ti₃Fe₂(OCH₂CH₂O)₉ were described. It was found that the synthesized Ti_{1 ? x} Fe _x O_{2 ? 2x/2} solid solutions exhibit photocatalytic activity in the reaction of hydroquinone oxidation in an aqueous solution on irradiation with UV light. A correlation between the rate of oxidation of hydroquinone and the concentration of iron in the catalyst was established. A procedure for the preparation of titanium dioxide with the structure of anatase doped with iron and carbon (Ti_{1 ? x} Fe _x O_{(2 ? x/2) ? yCy)} and also composites on its basis, which contain an excess amount of carbon, was proposed.     

Formation of helium cluster ions HHe x + (x≦14) and H3He x + (x≦13) in a very low temperature drift tube

The formation of cluster ions when hydrogen molecular ions H ₂ ⁺ and H ₃ ⁺ are injected into a drift tube filled with helium gas at 4.4 K has been investigated. When H ₂ ⁺ ions are injected, cluster ions HHe _x ⁺ (x≦14) are produced. No production of H₂He _x ⁺ ions is observed. When H ₃ ⁺ ions are injected, cluster ions HHe _x ⁺ (x≦14) are produced as well as H₃He _x ⁺ (x≦13), and very small signals corresponding to H₂He _x ⁺ (3≦x≦10) are observed. Information on the stability of HHe _x ⁺ and H₃He _x ⁺ is derived from the drift field dependence of the cluster size distributions. The cluster sizex=13 is found to be a magic number for HHe _x ⁺ , and for H₃He _x ⁺ ,x=10 and 11.     

New Ion Conductor of (Ba1−xLax)2In2O5+x

The structural characterization, thermogravimetric analysis and electrical properties for solid solution system, (Ba_1–xLa_x)₂In₂O_5+x with perovskite-type structure were investigated. X-ray diffraction showed that the orthorhombic phase was in the range of 0.0<x0.3, the tetragonal phase 0.3<x0.5, and the cubic phase 0.5<x. The sharp transition of electrical conductivity shifted to a lower temperature with increasing x and disappeared at the phase boundary between the orthorhombic and tetragonal phases. This perovskite-related oxide exhibited a pure oxide-ion conduction over the oxygen partial pressure range of 1 atm to 10^–3.5 atm, and the electrical conductivity reached the value of 1.610^–1 (S cm^–1) at 1073 K, which was nearly equal to that of the yttria stabilized zirconia. These properties were successfully explained in terms of disordered oxygen ions.This revised version was published online in November 2005 with corrections to the Cover Date.     

F+ and F⁻ affinities of simple N(x)F(y) and O(x)F(y) compounds

Atomization energies at 0 K and heats of formation at 0 and 298 K are predicted for the neutral and ionic N(x)F(y) and O(x)F(y) systems using coupled cluster theory with single and double excitations and including a perturbative triples correction (CCSD(T)) method with correlation consistent basis sets extrapolated to the complete basis set (CBS) limit. To achieve near chemical accuracy (±1 kcal/mol), three corrections to the electronic energy were added to the frozen core CCSD(T)/CBS binding energies: corrections for core-valence, scalar relativistic, and first order atomic spin-orbit effects. Vibrational zero point energies were computed at the CCSD(T) level of theory where possible. The calculated heats of formation are in good agreement with the available experimental values, except for FOOF because of the neglect of higher order correlation corrections. The F(+) affinity in the N(x)F(y) series increases from N(2) to N(2)F(4) by 63 kcal/mol, while that in the O(2)F(y) series decreases by 18 kcal/mol from O(2) to O(2)F(2). Neither N(2) nor N(2)F(4) is predicted to bind F(-), and N(2)F(2) is a very weak Lewis acid with an F(-) affinity of about 10 kcal/mol for either the cis or trans isomer. The low F(-) affinities of the nitrogen fluorides explain why, in spite of the fact that many stable nitrogen fluoride cations are known, no nitrogen fluoride anions have been isolated so far. For example, the F(-) affinity of NF is predicted to be only 12.5 kcal/mol which explains the numerous experimental failures to prepare NF(2)(-) salts from the well-known strong acid HNF(2). The F(-) affinity of O(2) is predicted to have a small positive value and increases for O(2)F(2) by 23 kcal/mol, indicating that the O(2)F(3)(-) anion might be marginally stable at subambient temperatures. The calculated adiabatic ionization potentials and electron affinities are in good agreement with experiment considering that many of the experimental values are for vertical processes.     

Mn(I) in an extended oxide: the synthesis and characterization of La(1-x)Ca(x)MnO(2+δ) (0.6 ≤ x ≤ 1)

Reduction of La(1-x)Ca(x)MnO(3) (0.6 ≤ x ≤ 1) perovskite phases with sodium hydride yields materials of composition La(1-x)Ca(x)MnO(2+δ). The calcium-rich phases (x = 0.9, 1) adopt (La(0.9)Ca(0.1))(0.5)Mn(0.5)O disordered rocksalt structures. However local structure analysis using reverse Monte Carlo refinement of models against pair distribution functions obtained from neutron total scattering data reveals lanthanum-rich La(1-x)Ca(x)MnO(2+δ) (x = 0.6, 0.67, 0.7) phases adopt disordered structures consisting of an intergrowth of sheets of MnO(6) octahedra and sheets of MnO(4) tetrahedra. X-ray absorption data confirm the presence of Mn(I) centers in La(1-x)Ca(x)MnO(2+δ) phases with x < 1. Low-temperature neutron diffraction data reveal La(1-x)Ca(x)MnO(2+δ) (x = 0.6, 0.67, 0.7) phases become antiferromagnetically ordered at low temperature.     

Effect of hydration on conductivity of Ba4La x Ca2 − x Nb2O11 + 0.5x (x = 0.5, 1, 1.5, 2) phases

Substitution of Ca by La in initial cubic double perovskite Ba₄(Ca₂Nb₂)O₁₁[VO]₁ allowed obtaining phases with a similar structure with a lower content of structural oxygen vacancies, Ba₄(La _x Ca_{2 ? x} Nb₂)O_{11 + 0.5x} [VO]_{1 ? 0.5x} (x = 0.5, 1, 1.5, 2). The impedance technique was used to measure the temperature dependences of conductivity in the atmosphere of dry and humid air. Transport numbers determined using the EMF method in an oxygen-air and water steam concentration cells point to the predominantly hole nature of conductivity in the high-temperature region (T > 600°C) and to predominance of proton conductivity in the low-temperature region. Activation energies of hole and proton conductivity were calculated. Thermogravimetric measurements were carried out under heating from 25 to 1000°C with simultaneous mass-spectrometric determination of evolved H₂O and CO₂. The properties of the studied Ba₄(La _x Ca_{2 ? x} Nb₂)O_{11 + 0.5x} (x = 0.5, 1, 1.5, 2) phases were compared with the earlier studied Ba_{4 ? x} La _x (Ca₂Nb₂)O_{11 + 0.5x} phases with similar lanthanum content.     

High resolution spectroscopy of the 13Σ g + (b) ← 13Σ u + (x) transition of Na2

Rotational-vibrational transitions of the triplet system 1³Σ _g ⁺ ← 1³Σ _u ⁺ of the Na₂ molecule have been investigated around $\bar v = 13970 cm^{ - 1} $ by Doppler-free polarization spectroscopy in a heat pipe and by resonant two-step photoionization in a collimated cold argon beam, seeded with sodium vapor. The fine- and hyperfine structure of the transitions is partly resolved. The analysis of the measured spectra and a theoretical discussion of the expected multiplet structure yields the rotational constantsB′ _v (v′=17)=0.0866(4) cm^?1 for the upper andB″ _v (v″=0)=0.0533(4) cm^?1 for the lower state. The difference Δb=b(³Σ _u )?b(³Σ _g ) of the hyperfine coupling constantsb turns out to be Δb=80 MHz.     

Ca_(1-x)Al_(2+x)Si_2O_8中Eu~(3+)和Eu~(2+)的发光行为研究

采用高温固相法制备Ca_(1-x)Al_(2+x)Si_2O_8:12%(摩尔分数)Eu~(3+)荧光粉,在紫外激发下得到红色与蓝色混合系列发光材料。通过调控Ca和Al的比例,结果显示:当x=0.3,即Ca_(0.7)Al_(2.3)Si_2O_8:Eu~(3+)为此发光材料的最佳比例,在λ_(ex)=296 nm激发下Eu~(3+)发光强度最大,λ_(ex)=319 nm激发下Eu~(2+)发光强度最大。有趣的是,在Eu~(3+)的五个特征峰中~5D_0→~7F_4(682 nm)的强度在之前的研究中没有出现与~5D_0→~7F_2(614 nm)相接近,但在我们的实验中观察到在296和319 nm激发下,~5D_0→~7F_4的发光强度与~5D_0→~7F_2已非常接近。通过监测682 nm与614 nm处的荧光寿命分别为1.99和1.84 ms,得出它们属于一个发光中心。通过色坐标的测量,此样品在蓝光区与红光区可进行调节,因此这种材料作为白光LED中的蓝色与红色荧光粉存在潜在的应用前景。     

Inhibitory effect of H_(3 + x)PMo_(12－x)V_xO_(40)-Ton the self-polymerization of methyl methacrylate

In this work,a series of molybdovanadophosphoric heteropoly acid quaternary ammonium salts H_(3+x)PMo_(12 -x)V_xO40-T were synthesized and employed as a reaction inhibitor in the selfpolymerization of methyl methacrylate(MMA).The polymerization inhibition effect of H_(3+x)PMoPMo_(12 -x)V_xO40-T)with different number of vanadium atoms and reaction dosages was investigated using differential scanning calorimetry(DSC).It shows that the inhibitory effect was improved with the increasing dosages of H_(3+x)PMoPMo_(12 -x)V_xO40-T),and the polymerization inhibition was also affected by the number of vanadium atoms in the H_(3+x)PMo_(12 -x)V_xO40-T .Furthermore,cyclic voltammograms(CV)was used to probe the mechanism of the inhibition reaction with H3+xPMo12xVxO40-T.The result of CV indicates that the inhibition reaction is an oxidation–reduction reaction.H_(3+x)PMo_(12 -x)V_xO40-T can react directly with the MMA monomer radicals,which eliminated the MMA monomers,and therefore the self-polymerization of the MMA can be effectively inhibited by H_(3+x)PMo_(12 -x)V_xO40-T.     

New anion-conducting fluorite-like solid solution Bi1 − x Te x (O,F)2 + δ (0.28 < x < 0.43) in the BiF3-BiOF-TeO2 system

A new fluorite-like solid solution, II-Bi_{1 ? x} Te _x (O,F)_{2 + δ}, was produced by solid-phase synthesis at 873 K with subsequent annealing, its concentration boundaries were determined, and a scheme of an isothermal (873 K) section of the BiF₃-BiOF-TeO₂ system was proposed. The new phase was characterized by X-ray powder diffraction, electron microscopy, and impedance spectroscopy. Making heterovalent substitutions simultaneously in the cation and anion sublattices, Te⁴⁺ ? Bi³⁺ and O^2? ? F^? allowed one to vary the tellurium cation content x (at constant anion nonstoichiometry δ) or the anion nonstoichiometry δ (at constant tellurium cation content x or constant fluoride ion content), which enabled one to describe the effect of these parameters on the properties of the solid solution. The anion excess δ was found to dominate the unit cell parameter of the solid solution and its ionic conductivity. The conduction within the studied temperature range was proven to be mainly by fluoride ions. It was assumed that the ordering of superstoichiometric anions, or clustering, can manifest itself as the structural modulations of the phase II-Bi_{1 ? x} Te _x (O,F)_{2 + δ} that were detected in this work.