(Ce_(0.8)RE_(0.2))_(1-x)M_xO_(2-δ)固体电解质的溶胶-凝胶合成及其电性质

利用溶胶 凝胶法合成了 (Ce0 .8RE0 .2 ) 1-xMxO2 -δ(RE :稀土 ,M :碱土 )系列固体电解质 ,XRD表明 80 0℃即形成萤石结构 ,较高温固相反应合成温度低约 70 0℃ .测定了样品的电导率和阻抗谱 .XPS测试表明 ,掺杂碱土氧化物后吸附氧浓度明显增大 ,氧空位增多 ,电导率和氧离子迁移数增大 ,改善了CeO2 基固体电解质的性能 .讨论了碱土及稀土离子对电性质的影响 .(Ce0 .8Sm0 .2 ) 1-0 .0 5 Ca0 .0 5 O2 -δ80 0℃时电导率0 1 2 6S·cm-1,氧离子迁移数 0 .99.

BaCe_(0.8)Ln_(0.2)O_(2.9)(Ln=Gd,Sm,Eu)固体电解质的低温制备及其燃料电池性质

利用溶胶 凝胶法低温合成了BaCe0 .8Ln0 .2 O2 .9(Ln =Gd ,Sm ,Eu)固体电解质 ,X射线粉末衍射表明 90 0℃即形成正交钙钛矿结构 ,较高温固相反应合成温度降低了约 6 0 0℃ .测定了样品的阻抗谱和电导率 ,研究了其导电机理 ,溶胶 凝胶法合成可减小或消除固体电解质的晶界电阻 ,80 0℃时BaCe0 .8Gd0 .2 O2 .9的σ =7.87× 10 -2S·cm-1,以它为电解质的氢氧燃料电池开路电压接近 1V ,最大输出功率密度为 30mW·cm-2 .

甲烷部分氧化制合成气研究进展

甲烷部分氧化制合成气是高转化率、高选择性、高空速、低H2／CO比、温和的放热反应，它很有希望代替常规的水蒸汽重整法。部分氧化催化剂虽有三类，但有应用价值的是活性组分Ni、Rh、Pt等为主的负载型催化剂。在常压或低压、600～9000℃、CH4／O2比1．6～2．0、空速大于105h-1的条件下，催化剂显示了较高的活性和选择性。关于反应机理，Prette、Schmidt及buyevskaya分别提出了三个不同的模型。催化剂的表面积炭问题也是甲烷部分氧化制合成气反应中的重要研究课题。

Studies on the adsorption property of NO on the Ni-based mixed oxide catalysts with Perovskite-like (ABO(3) and A(2)BO(4)) structure

The mixed oxides LaNiO3, La0.1Sr0.9NiO3, La2NiO4 and LaSrNiO4 with perovskite (ABO(3)) and related(A(2)BO(4)) structures were prepared and the adsorption property for NO and the catalytic activity for NO decomposition over these oxidse were also tested. The catalysts were characterized by means of BET surface measurement, chemical analysis, NO-TPD etc.. It was shown that the adsorption amount of NO is correlated with the concentration of oxygen vacancy formed and the adsorption type and strength of NO are related to the valence of metallic ion. Generally there are three kinds of adsorption species, NO-, NO+ and NO on the mixed oxides, among them the negative adsorpion species (NO-) are active for NO decomposition. The weaker the adsorption of oxygen on the catalyst is, the faster the mobility of oxygen is and the easier the redox process takes place in reproducing the active sites in which the oxygen species (O-, O2-) would participate.

旋转环盘电极研究氧在PolyCoPP膜上的电催化还原

用旋转环（Au）－盘（热解石墨，PG）电极研究了氧在聚钴原卟啉二甲酯膜（PolyCoPP）上的电催化还原．实验发现在0．1mol·L－1NaOH，O2饱和的溶液中，当盘电位在低极化区时，氧的还原主要是二电子还原过程，HO2－为主要产物，不会再进一步还原为OH－；而在高极化区时，氧既有四电子的直接还原，也有HO2－的进一步还原.

甲烷氧化偶联Ti-La-Li系多元氧化物催化剂的表面碱性和表面活性氧种

利用CO2-TPD方法考察了Ti-La-Li系多元氧化物催化剂的表面碱性,实验发现:C2 选择性与表面碱强度呈顺变关系,而CH4 转化率与CO2 的脱附峰面积呈顺变关系.同时,利用XPS,O2-TPD等方法对该体系催化剂的表面活性氧种进行了表征与研究,结果表明:催化剂的表面晶格氧与C2 选择性有关,表面吸附氧与甲烷转化(包括偶联和深度氧化)有关.O2 -TPD实验发现催化剂的表面存在三种氧:α( 100℃≤t≤450℃),β(450℃

RAPID-DETERMINATION OF KINETIC-PARAMETERS FOR THE ELECTROCATALYTIC REDUCTION OF DIOXYGEN BY VITAMIN-B12 ADSORBED ON GLASSY-CARBON ELECTRODE

In this paper, the electrochemical behavior of vitamin B-12, ie cyanocobalamin (abbr. VB12) in a weak acidic aqueous solution and adsorbed on glassy carbon (GC) surface (abbr. VB12(ad)/GC) in different pH buffer solutions have been described by using cyclic voltammetry (cv). It is found that VB12 and VB12(ad)/GC exhibit catalytic activity for the electroreduction of O2 according to two reduction peaks at -0.50 and -1.00 V vs. sce; but their electrocatalytic activity is very unstable. Based on the method of hydrodynamic amperometry [B. Miller and S. Bruckenstein, J. electrochem. Soc. 117, 1033 (1970)], some kinetic parameters for the electrocatalytic reduction of O2 by VB12(ad)/GC have been determined rapidly by using a linear rotation-scan method [Rongzhong Jiang and Shaojun Dong, Electrochim. Acta 35, 1451 (1990)]. These kinetic parameters indicate that the reduction of O2 on VB12(ad)/GC gives water predominantly in both potential ranges which correspond to those two reduction peaks. Possible reaction mechanisms have been suggested.

THE YELLOW-TO-BLUE INTENSITY RATION (Y/B) OF DY-3+ EMISSION

Various borates, vanadates, niobates, antimonates, titanates, zirconates and CaS doped with Dy3+ were prepared. Factors which have an effect on the yellow-to-blue intensity ratio (Y/B) of Dy3+ emission are reported. Y/B increases with decreasing Z/r or electronegativity of the next-neighbour element M in the complex oxides Dy-O-M. The greater the degree of covalency between Dy3+ and O2-, the greater Y/B is. When Dy3+ is located at a site with an inverse centre and high symmetry, Dy3+ displays no luminescence. It seems that Y/B of Dy3+ located at a site deviated from an inverse centre is greater than that of Dy3+ located at a site without an inverse centre. Y/B does not vary much with the variation in concentration of Dy3+ when Dy3+ is substituted for an element with the same valency, but it does depend on the concentration of Dy3+ when Dy3+ is substituted for an element with a different valency in the matrix, because defects are formed in this case.

CHARGE COMPENSATION AND VALENCY STABILITY OF EU(II)-DOPED KMGF3 CRYSTAL

The spectrochemistry of Eu2+-doped perovskite KMgF3 was examined and discussed. Eu2+ can replace some of the K+ in the KMgF3 crystal, and simultaneously the corresponding cation hole can be compensated with the F- or O2- in the matrix. The emission intensity of Eu2+ due to the f --> f transition increased when Na+, Rb+ or F- was doped in KMgF3:Eu2+. Two mechanisms of charge compensation were proposed. No obvious valence change of Eu2+ occurred in KMgF3:Eu2+ after calcinating at high temperature, e.g. 900-degrees-C. It was found that the valence stability of Eu2+ improved after incorporation into the matrix.

GAS PERMEABILITIES OF POLY(TRIMETHYLSILYLPROPYNE) MEMBRANES SURFACE MODIFIED WITH CF4 PLASMA

Surface fluorination of poly (trimethylsilylpropyne) (PTMSP) membranes by CF4 plasma was studied. The surface fluorination of the membranes was carried out in an atmosphere of CF4 in a capacitively coupled discharge apparatus with external electrodes. Dramatic increase in selectivity (P(O2)/P(N2)) was observed. The effect of fluorination conditions such as duration of treatment and discharge power on the permeabilities of the membranes was studied. X-ray photoelectron spectrometric data of modified PTMSP membranes showed a drastic alternation in the surface layer. The P(O2) and P(O2)/P(N2) of the membranes were observed to be dependent on the F/C atomic ratio. At F/C > 1, the P(O2/P(N2) value of the membranes could be more than four.

电子能谱法研究改性的聚丙烯纤维性能与结构关系

本文讨论了聚丙烯纤维（PPF）在Ar、N2、O2和空气等离子体作用时，改变时间和功率对PPF表面进行等离子体处理，发现处理后纤维的吸湿性变化很大，回潮率是未处理样品的120-400%，染色性能从5级提高到1级标准。这一变化的光电子能谱法研究结果表时：PPF表面的结构发生较大变化。表面大量引入含O、N极性基团。经谱图拟合可知，这些基团是亲水性的极性结构，应归属于C-OH、C=O、COOH、C-NH2和CONH2基团。

SOLID DEFECT STRUCTURE AND CATALYTIC ACTIVITY OF PEROVSKITE-TYPE CATALYSTS LA1-XSRXNIO3-LAMBDA AND LA1-1.333XTHXNIO3-LAMBDA

Two series of La1-xSrxNiO3-lambda and La1-1.333xThxNiO3-lambda catalysts have been prepared, and the relationships between the solid defect structure and catalytic activity for NH3 oxidation were measured. The results showed that in the range of x < 0.3, the samples possessed single perovskite-type structure, and as the content of Sr2+ decreased and that of Th4+ increased the catalytic activity increased which was paralleled with the Ni3+ concentration within the catalysts. The active oxygen species (O- or O2(2-)) were present not only on the surface but also in the bulk of the samples. The synergistic effect of transition metal ions with higher oxidation states and randomly distributed oxygen vacancies was the key factor determining catalytic activity of perovskite-type oxides. A redox mechanism for NH3 oxidation over ABO3 is proposed.

THE ACTIVE OXYGEN ON THE LI/LA2O3 CATALYST SURFACE AND ITS CATALYTIC BEHAVIOR IN THE OXIDATIVE COUPLING OF METHANE

The coupling selectivity was greatly enhanced by adding Li to La2O3, compared with the single La2O3. The O2- species was found on the Li/La2O3 but not on the single La2O3. In low-temperature desorption, ethane desorbed from the Li/La2O3 but was not detected with the single La2O3. It is considered that the addition of Li gave rise to some basic sites which are favorable for the coupling reaction.

ANALYSIS OF A NEW SUPERCONDUCTING PHASE IN THE BISRCACUO SYSTEM

By doping Sb, Ba and In to the Bi-system and with the variation of nominal atomic ratio of Cu, Sr and Ca, a new possible phase is found with T(c) almost-equal-to 105 K, but with a structure of 2212 phase. Effects of post-sintering treatment from air-quenched to O2-annealed were investigated for the approximately 105 K new phase.

三甲基硅烷基丙炔与五甲基二硅烷基丙炔共聚物膜及其气体透过性

研究了三甲基硅烷基丙块与五甲基二硅烷基丙块共聚物〔poly(TMSP-co-PMDSP)〕的成膜特点。poly(TMSP-co-PMDSP)膜的气体透过系数分别为:P_(O2):4×10~3～12×10~3,P_(N2):3×10~3～8×10~3和P_(CO2):2×10~4～4×10~4barrer,气体透过稳定性低,透过行为偏离第二Fick定律,过系数下降,其中溶解系数降低的比例远大于扩散系数的增加比例,在含有凝聚性气体的环境里,膜的气体透过出现表面吸附控制的特征。