相转移催化作用。负载型催化剂中反应位点的定位

J. Hradil, F. Švec, Č. Koňák, K. Jurek
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引用次数: 7

摘要

假设两相(PTC)和三相(TC L-S-L)催化之间没有基本的区别,因为在两种情况下,活性阴离子都必须从水相转移到有机相,而被置换的阴离子必须转移回水相,则证明了转移的可能途径。结果表明,固定在聚合物载体和无机载体上的催化剂的活性差别不大。反应速率与颗粒大小的关系及其与孔径大小的无关性证明了反应可能主要在催化剂的表面区域进行。实验数据似乎证明,表面反应的原因并不包括与底物扩散到反应位点相比相当高的反应速率。对Cu(II)离子的受控吸附和聚合物与只溶于有机相的试剂之间的反应结果的分析,可以通过观察颗粒的横截面来跟踪反应的过程,似乎支持这样一种观点,即催化剂的孔只被一种相(通常是连续的水相)填充,这有效地阻止了其他相扩散到颗粒中。
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Phase-transfer catalysis. IV. Localization of reaction sites in supported catalysts

Assuming that there is no basic difference between the two-phase (PTC) and three-phase (TC L-S-L) catalysis, as in both cases the active anion must be transferred from the aqueous phase into the organic phase and the displaced anion must be transferred back into the aqueous phase, possible routes of the transfer are demonstrated. It was found that the activities of catalysts immobilized on a polymer or inorganic carrier did not differ much from each other. The dependence of reaction rate on particle size and its independence of pore size are used to demonstrate that the reaction may proceed predominantly in the surface zone of the catalyst. Experimental data seem to prove that the cause of the surface reaction does not consist of a considerably higher reaction rate compared with the diffusion of the substrates to reaction sites. An analysis of the results of controlled sorption of the Cu(II) ion and of the reaction between the polymer and an agent soluble only in the organic phase, the course of which can be followed by observing the cross-section of the particle, seems to favour a view that pores of the catalyst are filled with one phase only (usually, the continuous aqueous phase), which effectively prevents diffusion of the other phase into the particles.

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