New protonic solid electrolyte with tetragonal tungsten bronze structure obtained through ionic exchange

Proton exchange reactions have been performed on tetragonal tungsten bronze-like NaNbWO₆ by using nitric acid as an exchanging agent. The characterization of the exchange reaction products has been made by means of chemical analysis, X-ray diffraction, thermal analysis, and IR spectroscopy. The exchange reaction takes place topotactically and the following formula is proposed for the obtained phase of variable composition: Na_1−xH_xNbWO₆·yH₂O (0<x?0.46 and 0?y?0.12). Impedance spectroscopy on the present proton exchanged samples indicated that these samples behaved as solid electrolytes under high humidity. As an example, the compound with the composition Na_0.68H_0.32NbWO₆·0.1 H₂O exhibits ionic conductivity of 8×10⁻³ and 1×10⁻² S cm⁻¹ at 70°C and 90°C, respectively.     

Hydrothermal synthesis of potassium molybdenum oxide bronzes: structure-inheriting solid-state route to blue bronze and dissolution/deposition route to red bronze

The hydrothermal syntheses of the alkali metal molybdenum bronzes from starting solids (H_xMoO₃) with structural affinities to the desired products were investigated. Single-phase potassium blue and red bronzes were prepared by the hydrothermal treatments at around 430 K, and characterized by powder X-ray diffraction, IR spectroscopy, and SEM. The formation processes of these two bronzes during the hydrothermal treatments were found to differ. The blue bronze was formed by a structure-inheriting solid-state route from H_xMoO₃ with x<0.3, whereas the red bronze was formed for x>0.3 through a solution dissolution/deposition route via the formation of MoO₃+MoO₂.     

Hydrothermal synthesis of one-dimensional (1D) Na<Subscript>x</Subscript>TiO<Subscript>2</Subscript> nanostructures

Nanorods of sodium titanium dioxide bronze Na_xTiO₂ were synthesized by the hydrothermal treatment of the amorphous TiO₂·nH₂O gel with 10 M NaOH followed by ultrasonication in 0.1 M HCl and thermal treatment (500°C, 10 h). The thermal treatment of the nanorods does not change the morphology of the particles. According to the electron diffraction data, the Na_xTiO₂ nanorods grow along the c axis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 71–73, January, 2005.     

Rare earth tungsten bronzes: a new method of synthesis. Perspectives for their application as inert matrices for transmutation of long-life actinide elements

A new method of synthesis of oxide tungsten bronzes containing lanthanide (Ln) Nd and Eu, based on thermal degradation of polyoxotungstate compounds, is proposed. The simplicity of the method allows to consider this class of compounds with chemical formula, Ln_xWO₃, as potential inert target for incineration or transmutation of minor actinides, Am and Cm, in neutron reactors. Nd and Eu were used as analogues of transplutonium elements. Powder X-ray diffraction patterns of compounds synthesized reveal a cubic perovskite structure. The lanthanide content in bronzes was determined by optical spectroscopy analysis. The experimental density of the pressed bronze samples was estimated at 6.58 g cm⁻³, i.e., 89% of the crystallographic value. The thermal stability of the bronzes synthesized was checked up to 900°C in an inert atmosphere. Leaching tests were performed for europium bronzes in nitric acid solutions using luminescence technique.     

稀土钨青铜K0.71Nd0.028WO3的制备及其电性能

Tetragonal tungsten bronze K_0.71Nd_0.028WO₃ was synthesized by rare earth co-permeation method using Keggin type POMs of α-K₁₀[SiCu₃(OH₂)W₉O₃₇]·6H₂O (abbreviated as SiW₉Cu₃) as precursor. XRD, XPS, XRF, TG-DTA were used to characterize the resulting material. The XPS results indicate that Nd has permeated and diffused into the body of the sample and exists in tungsten bronze in the form of K_0.71Nd_0.028WO₃. The results of TG-DTA show that K_0.71Nd_0.028WO₃ begins to decompose at 320 ℃. The consequence of DC four-probe shows that the conductivity of the sample permeated by rare earth is 10³ times higher than that of the sample only permeated by methanol at room temperature. The conductivity of the sample only permeated by methanol is only 10^-3 S·cm^-1 but the conductivity of the sample permeated by rare earth is 1.65 S·cm^-1.     

Characterization of the patina formed on a low tin bronze exposed to aqueous hydrogen sulfide

The dark gray corrosion layer (patina) formed on the surface of a polished low tin bronze alloy following exposure to a deoxygenated and saturated aqueous solutions of H₂S has been characterized by X‐ray photoelectron spectroscopy, scanning electron microscopy‐energy dispersive spectroscopy and X‐ray diffraction. The system represents a model for bronze corrosion in reducing conditions where sulfate‐reducing bacteria in soils or deoxygenated seawater may generate H₂S during respiration. The initial surface was dominated by metallic copper together with Sn, Pb and Zn oxides and hydroxides. Surface enrichment of Pb and Zn was noted because of a smearing effect during polishing. At least some of the lead was crystalline. In contrast, the corrosion layer formed by H₂S(aq) exposure was dominated by polycrystalline Cu₂S (low and high chalcocite) and smaller concentrations of CuSO₄ · nH₂O. This surface was enriched with Zn as Zn(OH)₂. Lead was present as redeposited PbS (galena) crystallites in at least two different morphologies. Unlike bronzes exposed to oxidizing conditions, which develop protective SnO₂ layers, the H₂S(aq)‐exposed surface was considerably depleted in Sn. Copyright © 2014 John Wiley & Sons, Ltd.     

Operando XAFS on Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn-ion Storage

Multivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn-ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in situ near-edge (XANES) and X-ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, Ca_xV₂O₅-H₂O (CVO), was probed at the V-K absorption edge. This operando study reveals the local electronic and geometric structure changes for CVO during galvanostatic cycling as the active material in an aqueous Zn-ion cell. The XANES data provides a fine resolution to track the evolution of the vanadium oxidative state and near-neighbor coordination sphere showing subtle shifts and delocalized charge. The Zn-ion influence on the V-K absorption edge is visualized using a difference technique called Δμ. Coupled with theoretical calculations and modelling, the extended region extracted local bonding information further confirms excellent electronic and structural reversibility of this vanadium oxide bronze in an aqueous Zn-ion electrochemical cell.     

AMT在青铜器文物表面形成缓蚀膜的计算分析

利用密度泛函(DFT)、概念DFT、Electron Localization Function(ELF)和Fukui函数中的亲电反应函数及Multiwfn软件,在B3LYP/6-311+G(d,p)基组水平上研究了5-氨基-2-巯基-1,3,4-噻二唑[AMT(a)]及其同分异构体[AMT(b)]和四面体型配合物i Thiol-Cu-2AMT的几何构型和反应特性.通过计算研究发现,首先AMT(b)与青铜器表面的Cu2+形成平面型配合物i Thiol-Cu后再与AMT(b)相互作用,并最终形成不规则的四面体型i Thiol-Cu-2AMT.在i Thiol-Cu-2AMT中Cu19能与AMT(b)中的亲核性原子有效地结合,形成四面体结构后将Cu19离子保护起来,达到了保护青铜器不受腐蚀的目的;对i Thiol-Cu-2AMT结构中的活性位置分析及ELF拓扑研究后发现,在i Thiol-Cu-2AMT中N6、N15、S26和S35原子又可以与其它的Cu2+相互作用,逐步形成配位型聚合物保护膜[i Thiol-Cu-2AMT]n.     

Li/富锂钒青铜(Li_6V_6O_(15))二次电池正极材料研究

近年来,人们对二次锂电池的正极进行了不少研究。许多过渡金属氧化物或硫化物,如V_6O(13),Li_(1+x)V_3O_8,TiS_2,MoS_2等被认为是较好的正极材料。Pistoia等研究了Li_(1+x)V_3O_8钒青铜的电化学性能得出,当Li浓度高时,由于电子定域作用使电荷屏蔽效应     

新铌酸盐Ba5NdTi3Nb7O30的合成与介电性能

The New Niobate Ba₅NdTi₃Nb₇O₃₀ was synthesized by solid state reaction at 1250℃ for 48h. The crystal structure and dielectric properties of Ba₅NdTi₃Nb₇O₃₀ were determined by X-ray powder diffraction and dielectric measurements. The results show that Ba₅NdTi₃Nb₇O₃₀ belongs to ferroelectric phase of tetragonal tungsten bronze structure at room temperature with unit cell parameters: a=1.24424(4)nm, c=0.39476(2)nm, calculated density 5.719g·cm^-3. Ba₅NdTi₃Nb₇O₃₀ belongs to relaxor ferroelectrics. The phase transition temperature (T_c) of Ba₅NdTi₃Nb₇O₃₀ from ferroelectric to paraelectric is found to shift toward higher temperature side at higher fre-quency, and T_c is 90℃ at 1kHz. At room temperature, the dielectric constant (ε_r) and dielectric loss of Ba₅NdTi₃Nb₇O₃₀ decrease with the increase of frequency, and Ba₅NdTi₃Nb₇O₃₀ ceramic have high dielectric constant 489 at 1kHz.