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本文研究了金属离子,特别是铈离子在叔-丁基过氧化氢分解反应中的催化性能。实验结果表明,金属离子对过氧化氢的分解能力不仅与金属离子的氯化还原电位有关,而且与金属离子的催化活性有密切的关系。根据在铈离子存在下的叔-丁基过氧化氢分解动力学的研究,提出如下机理: [Ce~(3+)ROOH)_3]→Ce~(4+)(ROOH)(OH~-)+RO~* Ce~(4+)(ROOH)(OH~-)→Ce~(4+)+H_2O+RO_2~*反应可能是通过电子转移而完成的,并伴随着金属离子的价态变化。这一看法已为紫外可见光谱的结果所证实。
In this paper, the catalytic performance of metal ions, especially cerium ions, in t-butyl hydroperoxide decomposition was studied. The experimental results show that the ability of metal ions to decompose hydrogen peroxide is not only related to the chloride reduction potential of metal ions but also closely related to the catalytic activity of metal ions. According to the study of the decomposition kinetics of t-butyl hydroperoxide in the presence of cerium ions, the following mechanisms are proposed: [Ce ~ (3+) ROOH) _3] → Ce ~ (4 +) (ROOH) + RO ~ * Ce ~ (4 +) (ROOH) (OH ~ -) → Ce ~ (4 +) + H_2O + RO_2 ~ * reaction may be accomplished by electron transfer accompanied by valence change of metal ions . This view has been confirmed by UV-visible spectroscopy results.