Nafion~/TiO_2复合膜的质子传导性能研究

0引言Nafion○膜是质子交换膜燃料电池和直接甲醇燃料电池的首选电解质膜。该膜若要成功地应用于燃料电池,还需要解决2个关键问题:降低甲醇渗透率和提高Nafion○膜在高温的质子传导能力(即保水能力)。目前主要靠在Nafion○膜的球状胶束中加入亲水性的无机纳米粒子解决这个问题[1￣9]。无机粒子的加入不仅可以有效地阻隔甲醇分子,而且因其亲水性可增加Nafion○膜在较高温度下的保水能力,使得Nafion○膜在较高温度仍可保持良好的质子导电性。以TiO2作为无机掺杂剂改善Nafion○膜的性能研究已有报道。Watanabe和Uchida等人[2,8]利用Pt的催…     

菜花状纳米氧化锌的溶剂热合成及气敏性能研究

以Zn(NO₃)₂·6H₂O和NaOH为原料,采用溶剂热合成技术制备了菜花状氧化锌纳米粉体,采用X射线衍射仪、扫描电镜和X-射线光电子能谱仪等对产物的物相、微观形貌和表面元素状态进行了表征,结果表明产物属于六方晶系的ZnO,呈规则的菜花状,分散性好,粒径90～100 nm,粉体表面存在大量的吸附氧。用该粉体制成厚膜型旁热式气敏元件,测试结果发现：在加热电压为6 V时气敏元件对甲醇、乙醇、正丙醇、丙酮、苯和甲苯等还原性气体具有较高的灵敏度,特别是对正丙醇、丙酮有较好的选择性,可以检测浓度低至1 μL·L^-1的乙醇、正丙醇和丙酮。     

4-羧基苯氧乙酸锰配位聚合物[Mn(p-CPOA)(H_2O)_3]_n的合成与晶体结构

0引言由于羧酸化合物具有丰富的配位结构类型,而且羧酸桥联多核配合物广泛存在于生物体内金属蛋白和金属酶的活性部位,使其在配位化学中占有重要地位[1]。尤其是近年来,研究发现羧酸配位聚合物具有潜在的光学、磁学、吸附分离、信息储存以及催化等性能,使得由苯二甲酸,均苯三甲     

具有不同形貌和择优取向的MxWO3·xH2O粉晶的制备与表征

采用沉淀结合渗析的方法，以钨酸钠、钨酸铵为原料，制备了不同形貌、具有择优取向的M_xWO₃·xH₂O(M=Na⁺，NH₄⁺，x<1)粉晶，利用SEM、XRD、TG、IR、XPS等手段对粉体进行表征，考察了不同渗析时间和焙烧温度对粉晶形貌、晶化程度及结构转变的影响。结果表明，长时间渗析后粉体的晶化程度明显提高，并沿(010)晶面方向择优生长，形貌由不规则形变为梭形和蝴蝶形。经空气气氛400 ℃焙烧后，Na_xWO₃·xH₂O和(NH₄)_xWO₃·xH₂O粉晶均转变为沿(200)晶面方向择优生长的立方青铜相，且形貌也发生改变。     

钒氧配合物[VOL(C9H6NO)]·CH2Cl2的合成与晶体结构

A oxovanadium(Ⅴ) complex of [VOL(C₉H₆NO)]·CH₂Cl₂[H₂L=2-hydroxy-1-naphthaldehyde 4-methoxy-benzoylhydrazone, C₉H₆NO^-=8-hydroxyquinoline anion] has been synthesized and characterized by elemental analyses, IR and single crystal X-ray diffraction. The crystal crystallizes in triclinic system, the space group is P1, with the crystal cell parameters a=1.087 0(2) nm, b=1.107 1(2) nm, c=1.269 3(3) nm, α=67.84(3)°, β=79.26(3)°, γ=73.85(3)° and V=1.353 1(6) nm³ , M_r=614.34, R=0.0503, wR=0.1409. The V(Ⅴ) atom is six-coordinated by one O atom of oxo group, two O atoms and one N atom of the tridentate hydrazone ligand, as well as one N atom and one O atom of 8-hydroxyquinoline ligand, thus defining a distorted octahedral VO(ONO)(NO) geometry. A two-dimensional supramolecular layer structure is formed through π-π stacking interactions. CCDC: 268672.     

Nafion? / TiO2复合膜的质子传导性能研究

Nafion^® / TiO₂ composite membranes were prepared by in-situ chemical reaction method using Ti(OC₄H₉)₄ and Nafion^® 117 as raw materials. The membranes were characterized by UV, FTIR-ATR and XRD, respectively. Methanol permeability and water uptake were investigated as a function of TiO₂ contents. The conductivity of the membranes was measured under water vapor pressure (2.644 7 kPa) or in dry atmospheres. The XRD results showed that the titanium dioxide in Nafion^® membranes were crystallized in anatase phase with an average crystaline diameter of 3.0 nm. The water uptake of the composite membranes was larger than that of the pure Nafion^® membrane when the TiO₂ loading was within 14wt%. The methanol permeability of the membrane decreased as the TiO₂ loading increased. The addition of 3wt% TiO₂ to Nafion^® membranes improved the conductivity in dry measurement conditions. The proton conductivity of the composite membrane increased greatly after the hydrothermal treatment at 160 ℃ for 2 hours.     

Ca2-3xLa8+2x□x(SiO4)6O2的合成及其导电性能的研究

The silicate oxyapatites Ca_2-3xLa_8+2x□_x(SiO₄)₆O₂(x=0, 0.17, 0.33, 0.50, 0.67) was synthesized via a sol-gel method at low temperature. The apatite phases have been characterised by X-ray diffraction (XRD), conducting properties was studied by electrical chemistry impedance spectroscopy (EIS). The conductivity of La_9.33□_0.67(SiO₄)₆O₂ is 1.58×10^-3 S·cm^-1 at 700 ℃, it is higher about 4 270 times than that of Ca₂La₈(SiO₄)₆O₂, the activation energy is decreasing from 1.37 eV to 0.84 eV. With cation vacancies increasing,the conducting mechanism is gradually translation from a direct linear pathway free oxygen ion conduction to a curve pathway interstitial oxygen ion conduction. The electrical conductivities is almost independent of the oxygen partial pressure, this suggests that the oxyapatites exhibited almost pure O^2- ion conduction over a wide range of oxygen partial pressure.     

一维链状4-羧基苯氧乙酸桥联钴配位聚合物[Co(p-CPOA)(2，2′-bipy)(H2O)]n的合成与晶体结构

A novel coordination polymer of [Co(p-CPOA)(2，2′-bipy)(H₂O)]_n (p-CPOA^2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction. The title complex crystallizes in monoclinic space group C2/c, with a=1.424 4(3) nm, b=1.316 6(3) nm, c=1.947 7(4) nm, β=104.56(3)°. V=3.535 3(14) nm³, Z=8, R=0.028 5, wR=0.089 1. The cobalt(Ⅱ) ion displays a distorted octahedral coordination geometry, defined by three carboxyl oxygen atoms from different p-CPOA^2- groups, two nitrogen atoms from 2,2′-bipyridine ligand and one water molecule. The cobalt atoms are bridged by p-CPOA^2- groups, forming a one-dimensional chain structure along a axis. The adjacent Co…Co atoms distance is 0.996 8 nm. A layer supramolecular network is contrsucted by the hydrogen bonds and π-π stacking interactions. CCDC: 220039.     

EDTA 介质中元素的 ICP-MS行为研究

研究了在EDTA介质中元素的ICP－MS质谱行为，探讨了在不同质谱条件下，EDTA的引入对不同元素分析信号的影响，结果表明：EDTA的引入对元素分析信号有不同程度的增强效应，氧化物产率明显降低，对轻质量元素^9Be,^59Co信号增强的100％，中质量元素^115In,^159Tb信号增强约20％，重质量元素^209Bi,^238U信号变化不明显：LaO^ /La^ ,CeO^ /Ce^ 产率降低约10％，与通常2％HNO3介质的溶液相比，在相同入射功率条件下，EDTA介质中信号达最佳时，需采用稍低的雾化气流速，实验了以有机酸形式引入钠盐对元素分析信号的影响。     

中温固体氧化物燃料电池复合阴极材料LSM-CBO的制备及性能研究

采用柠檬酸络合法为中温固体氧化物燃料电池制备了La0 .85Sr0 .15MnO3 Ce0 .7Bi0 .3 O2 (LSM CBO)复合阴极材料 ,利用XRD和SEM对材料进行了表征 .结果表明该复合材料在 10 0 0℃以内烧结时不发生反应 ,且在 90 0℃烧结 2h条件下 ,电极与Ce0 .9Gd0 .1O2 (CGO)电解质可形成良好的接触 .复合电极在 70 0℃ ,0 .6V阴极极化电势下处理 96h ,也没有发现可检测到的其它物相 .我们同时使用交流复阻抗谱和直流极化技术研究了电极的电化学性能 ,结果表明氧在电极表面的吸附是阴极反应的速率控制步骤 ,且随着CBO含量的增加电极极化电阻减小 ,最小值达到 2 2 3Ω·cm2 ,出现在掺杂 3 0wt %CBO的LSM复合电极中