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化学学报
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化学学报 ›› 1991, Vol. 49 ›› Issue (8): 788-792. 上一篇    下一篇

研究论文

杂多阴离子的XPS研究 II:Keggin结构钨钼杂多酸热稳定性差异的研究

王占文;吴乃钧;方景礼   

  1. 南京化工学院应化系;南京大学大学系
  • 发布日期:1991-08-15

Studies of heteropolyanion by XPS.II.SPS study on the difference of thermostability between 12-heterotungstic and molybdic acids

WANG ZHANWEN;WU NAIJUN;FANG JINGLI   

  • Published:1991-08-15

PDF

666

被引次数

20

加入优级纯CsCl作内标,用其中Cs3d5/2校正荷电效应,准确地测定了HPWnMo12-n(n=0,3,6,9,12)及HXM12(X=P,As,Si,Ge;M=W,Mo)中Ols及HPM12中P2p的结合能,发现钨系中Ols的结合能比钼系中的高约0.5eV;P2p的结合能则相应地高0.8eV;同种金属的磷系杂多酸中Ols的结合能比其他杂原子中的高0.3eV。通过差热分析发现同类型杂多酸的热稳定性与阴离子中的Ols结合能呈近似平行的关系。结果表明,跟钼系杂多酸相比,钨系杂多酸中氧原子有较低的电子云密度,钨氧之间有更多的轨道重叠;含磷杂多酸跟其他杂多酸相比,金属、氧之间有更强的相互作用。

关键词: 红外分光光度法, 杂多酸, 钼酸盐, 磷酸盐, 络合物, 内标, 热稳定性, 电子密度, 差热分析, 钨酸盐

The binding energies of oxygen 1s and heteroatoms (P) in PWnMo12-n (n = 0, 3, 6, 9, 12) and XM12 (X = P, Asw, Si, Ge; M = W, Mo) were determine by adding highly pure CsCl as an internal label using Cs3d5/2 to calibrate the charge effect. The O1s and P binding energies in heterotungstic acids were higher by 0.5 eV and 0.8 eV, resp., than those in heteromolybdic acids, and the O1s binding energies in PM12 were 0.3 eV higher than those in other heteroatom's. The thermal stability of the heteropoly acids was closely paralleled to the variation of the O1s binding energy. Compared with XMo12, the electron d. of oxygen was lower and the overlap of the orbits between M and O was more effective in XW12, and that the interreaction between M and O in PM12 was stronger than that in other XM12.

Key words: INFRARED SPECTROPHOTOMETRY, HETEROPOLYACID, MOLYBDATE, PHOSPHATE, COMPLEX COMPOUNDS, INTERNAL STANDARD, THERMAL STABILITY, ELECTRON DENSITY, DIFFERENTIAL THERMAL ANALYSIS, TUNGSTATE

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