高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (5): 658.

• 研究论文 • 上一篇    下一篇

SO42-/ZrO2超强酸体系红外光谱研究

高滋, 陈建民, 唐颐   

  1. 复旦大学化学系, 上海 200433
  • 收稿日期:1992-03-23 修回日期:1993-01-13 出版日期:1993-05-24 发布日期:1993-05-24
  • 通讯作者: 高滋
  • 基金资助:

    中国石油化学工业总公司资助课题

Infrared Studies of SO42-/ZrO2 Superacid System

GAO Zi, CHEN Jian-Min, TANG Yi   

  1. Department of Chemistry, Fudan University, Shangttai, 200433
  • Received:1992-03-23 Revised:1993-01-13 Online:1993-05-24 Published:1993-05-24

摘要: 用IR光谱研究了SO42-/ZrO2超强酸体系脱水和脱吡啶过程中的结构变化,实验结果表明,含水样品的表面硫物种中SO键呈离子键(Ⅰ)和共价双键(Ⅱ)两种形式,随脱水程度增加,Ⅰ逐渐变成Ⅱ。吸附吡啶样品的SO键亦有Ⅰ、Ⅱ两种形式,且随脱吡啶程度增加,Ⅰ逐渐变成Ⅱ。在脱水或吡啶过程中,SO键Ⅱ的振动频率移向高频,表明SO键键级增加,共价性质加强。无水的SO42-/ZrO2样品表面只有L酸位,无B酸位。吸水后部分L酸位可按1:1转变成B酸位,但体系中L酸量始终高于B酸量。根据键级、键长和氧电荷计算结果,还讨论了样品吸水后产生的B酸位结构。

关键词: SO42-体系, 超强酸, L酸, B酸, 结构

Abstract: Structural changes in the SO42-,/ZrO2 superacid system caused by desorption of preadsorbed water and pyridine were studied with IRspectroscopy.The experimental observations show that SObonds in the surface sulfur species of the hydrated samples exist in two forms, i, e., the ionic SObond (Ⅰ) and the covalent SOdouble bond(Ⅱ).Ⅰ transforms into Ⅱ with the removal of water from the sample.The presence of two types of SObonds and the transformation from Ⅰ to Ⅱ were also observed in samples preadsorbed with pyridine.In addition, the asymmetric stretching frequency of SObond Ⅱ shifts to a higher frequency during desorption of preadsorbed water or pyridine, suggesting that the bond order and the double-bond character of the SObond are increased.It is found that only Lacid sites are present on the surface of the carefully dried SO42-/ZrO2 sample.After adsorbing water, some Lacid sites may transform into Bacid sites in the ratio of 1:1.However, the number of Lacid sites in the sample is always higer than that of Bacid sites.The structure of the Bacid sites formed after hydration has been discussed by using the results of changes in bond order, bond length and partial charge on oxygen.

Key words: SO42-/ZrO2 system, Superacid, L acid, B acid.Structure

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