La_(1-x)Nd_xCrO_3(0.0≤x≤1.0)的化学键参数计算

使用复杂晶体化学键理论计算了La1-xNdxCrO3 (x =0 .0 ,0 .2 ,0 .4,0 .6 ,0 .8,1.0 )的化学键参数 ,如键性、键极化率等。结果表明 ,La-O ,Nd -O和Cr-O键的共价性基本上不随Nd掺杂的变化而变化 ,这个结论与实验结果一致。键极化率和磁距则随着掺杂量的增加而增加。共价性的大小次序为La -O

Preparation, characterization of solid solution La4BaCu5-xMnxO13+lambda (x=0-5) and its catalytic activity in the reduction of NO by CO

A series of layered mixed oxides La4BaCu5-xMnxO13+lambda(x = 0-5) was prepared, characterized and used as catalysts for NO+CO reaction. It was found that all the samples were single phase having a structure with five-layered-perovskite. La4BaCu2Mn3O13+lambda showed the highest activity in the title reaction, this could be attributed to the synergetic effect between Cu and Mn. The results of TPR, TPD and excess oxygen investigations confirmed that the Cu ion would be the active center. The displacement of the Cu ion by Mn caused the Cu ion to be more easily reducible and more content of excess oxygen, and it was beneficial to the activity of the catalyst. The reaction mechanism was also proposed.

Calculation of chemical bond parameters in La1-xCaxCrO3 (0.0 <= x <= 0.3)

The chemical bond parameters, that is, bond covalency, bond susceptibility, and macroscopic linear susceptibility of La1-xCaxCrO3 (x = 0.0, 0.1, 0.2, 0.3) has been calculated using a semiempirical method. This method is the generalization of the dielectric description theory proposed by Phillips, Van Vechten, Levine, and Tanaka (PVLT). In the calculation of bond valence, two schemes were adopted. One is the bond valence sums (BVS) scheme, and the other is the equal-valence scheme. Both schemes suggest that for the title compounds bond covalency and bond susceptibility are mainly influenced by bond valence and are insensitive to the Ca doping level or structural change. Larger bond valences usually result in higher bond covalency and bond susceptibility. The macroscopic linear susceptibility increases (only slightly for BVS scheme) with the increasing Ca doping level. (C) 1999 John Wiley & Sons, Inc.

LaC_4~n(n=-2,-1,0,+1,+2)分子簇的结构与稳定性

本文用密度泛函方法研究了LaC4n(n=-2,-1,0,+1,+2)分子簇的结构与稳定性。振动频率分析表明，在所提出的九个构型中，当ｎ＝-2，0，+1，+2时，稀土位于碳环上最稳定，而当ｎ＝-1时，尽管稀土位于碳环上能量最低，但没有找到稳定的构型，我们的结果还指出，稀土元素是分子簇中对外部环境最敏感的部位，即最具有反应活性

(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 .

Investigation of Pr valence and relationship between bond covalency and T-c in Y1-xPrxBa2Cu3O7 (x = 0-1)

The valence of Pr and relationship between bond covalency and T-c in Y1-xPrxBa2Cu3O7 (x = 0-1) have been studied using complex chemical bond theory. The results indicate that the depression of superconductivity in Y1-xPrxBa2Cu3O7 can be reasonably explained by bond covalency difference for the bonds between CuO2 plane and CuO chain. T-c decreases with the decreasing of bond covalency difference and reaches zero when bond covalency difference is zero (or bond covalency in CuO2 exceeds that in CuO chain) at Pr concentration 0.55 and valence +3.30. These are in good agreement with the experiments and meanwhile suggest that the valence of Pr is + 3.30 in Y1-xPrxBa2Cu3O7. The results also indicate that for Pr valence less than +3.15, superconductivity always exists for whatever Pr concentration, whereas for Pr with a valence of +4.0, superconductivity disappears as soon as Pr concentration exceeds 0.19. This supports with the viewpoint that higher valence Pr will contribute more electrons to CuO2 plane, filling the mobile holes responsible for conduction. For PrBa2Cu3O7 with no Ba-site Pr, our calculation suggests that it will be a superconductor if the average valence of Pr is less than +3.15. (C) 1998 Published by Elsevier Science B.V. All rights reserved.

Dependence of superconducting temperature on chemical bond parameters in YBa2Cu3O6+delta (delta=0-1)

The chemical bond parameters, that is ionicities and average energy gaps, for all types of chemical bonds in YBa2Cu3O6+delta have been investigated with variation of oxygen content delta (delta = 0.0, 0.35, 0.45, 0.58, 0.64, 0.73, 0.78, 0.81, 0.95, 1.00). The theory used is the complex crystal chemical bond theory, which is the development of P-V-L theory. The two plateaus near 90 K and 60 K in superconducting transition temperatures, and the disappearance of superconductivity with the change of oxygen content, were reasonably explained by chemical bond parameters. The results also showed that the Cu-O chains play a vital role in the transition from non-superconductors to superconductors, and the highest transition temperature occurred when the plane-chain reached a coupling state. (C) 1998 Elsevier Science Ltd. All rights reserved.

Theoretical investigation of LaC3n+ (n = 0, 1, 2) clusters by density functional theory

LaC3n+ (n = 0, 1, 2) clusters have been studied using B3LYP (Becke 3-parameter-Lee-Yang-Parr) density functional method. The basis set is Dunning/ Huzinaga valence double zeta for carbon and [2s2p2d] for lanthanum, denoted LANL1DZ. Four isomers are presented for each cluster; two of them are edge binding isomers with C-2 upsilon symmetry, the other two are Linear chains with C-infinity upsilon symmetry. Meanwhile, two spin states for each isomer, that is, singlet and triplet for LaC3+, doublet and quartet for LaC3 and LaC32+, respectively, are also considered. Geometries, vibrational frequencies, infrared intensities, and other quantities are reported and discussed. The results indicate that at some spin states; the C-2 upsilon symmetry isomers are the dominant structures, while for the other spin states, linear isomers are energetically favored. (C) 1998 John Wiley & Sons, Inc.

La_(0.2)Ca_(0.8)MnO_3催化剂活性相的结构和形成机理

利用TG，DTA，XRD和XPS方法研究了La0.2Ca0.8MnO3催化剂的结构和形成机理．样品用La，Ca，Mn混合硝酸盐制备．随着焙烧温度的升高发生了一系列的固相反应，发现氨氧化催化剂催化活性与生成的CaMnO3含量成正比．在900℃制备的含有CaMnO3，La0.575Ca0.425MNO3，Mn2O3和La2O3的混合物是氨氧化最佳催化剂，活性相是CaMnO3，并具有大量的氧空穴.

BaCe_(1-x)RE_xO_(3-0.5x)的溶胶 - 凝胶法合成及离子导电性

用溶胶－凝胶法合成了系列钙钛矿结构的ＢａＣｅ１－ｘＲＥｘＯ３－０．５ｘ（ＲＥ＝Ｌａ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，Ｈｏ，Ｅｒ和Ｙ）复合氧化物，通过ＸＲＤ和热分析对样品结构及生成过程进行了研究．测定了不同温度下样品的交流阻抗谱，讨论了稀土离子掺杂对ＢａＣｅＯ３电性质的影响．溶胶－凝胶法比固相反应法合成温度降低了６００～８００℃，稀土掺杂使ＢａＣｅＯ３离子导电率提高了１０～４０倍.

Structure, Stability and Vibrational Spectra of LaC_5~n(n=-1,0,+1) Clusters

用密度泛含方法研究了ＬａＣ５ｎ（ｎ＝－１，０，＋１）分子簇的结构和稳定性及振动光谱，对这个六原子体系提出了三种可能构型，点群结构为Ｃ２ｖ对称性．第一个构型为Ｌａ接在弯曲的Ｃ５链上，第二个是Ｌａ通过二个键与Ｃ５环相连第三个是Ｌａ通过一个键与Ｃ５环相连；结果表明，第一个构型即当Ｌａ接在弯曲的Ｃ５链上时能量最低．振动光谱分析指出，当ｎ＝－１时，第二个构型为局域极小值；当ｎ＝＋１时，第一个和第二个构型为局域极小值；对ｎ＝０，局域极小值没有找到.

Theoretical Investigation of LaC~n and La_2C~n(n=-1,0,+1)Clusters

用密度泛函方法研究了ＬａＣｎ及Ｌａ２Ｃｎ（ｎ＝－１，０，＋１）分子簇的结构和稳定性．对Ｌａ２Ｃｎ体系，提出了两种可能构型，其中一种具有Ｃ２ｖ对称性，另一种具有Ｄ∞ｈ对称性．计算结果表明，对Ｌａ２Ｃｎ，当ｎ＝＋１，－１时，线状结构最稳定，并且在ｎ＝＋１时，Ｃ２ｖ结构极不稳定有收敛向线状结构的趋势．而当ｎ＝０时，Ｃ２ｖ结构最稳定．最后还计算了ＬａＣ和Ｌａ２Ｃ分子簇的电子亲和势和离化能.

La_(0.9)Ni_2储氢合金的电化学性能

本文研究了稀土AB_2型非整比储氢合金La_(0.9)Ni_2的结构和电化学性能。结果表明,与LaNi_2储氢合金相比,La_(0.9)Ni_2合金显示了更易活化、更高的放电容量和突出的倍率性能,但荷电保持率较低。此外,合成工艺,退火处理和球磨对储氢合金的电极性能有很大影响。