氢铵
化学
环己醇
反应性(心理学)
沸石
无机化学
离子键合
催化作用
离子
分子
反应速率
物理化学
光化学
有机化学
医学
替代医学
病理
作者
Sung Min Kim,Feng Chen,Donald M. Camaioni,Miroslaw A. Derewinski,Oliver Y. Gutiérrez,Yue Liu,Johannes A. Lercher
摘要
In the presence of water, hydronium ions formed within the micropores of zeolite H-BEA significantly influence the surrounding environment and the reactivity of organic substrates. The positive charge of these ions, coupled with the zeolite's negatively charged framework, results in an ionic environment that causes a strongly nonideal solvation behavior of cyclohexanol. This leads to a significantly higher excess chemical potential in the initial state and stabilizes at the same time the charged transition state in the dehydration of cyclohexanol. As a result, the free-energy barrier of the reaction is lowered, leading to a marked increase in the reaction rates. Nonetheless, there is a limit to the reaction rate enhancement by the hydronium ion concentration. Experiments conducted with low concentrations of reactants show that beyond an optimal concentration, the required spatial rearrangement between hydronium ions and cyclohexanols inhibits further increases in the reaction rate, leading to a peak in the intrinsic activity of hydronium ions. The quantification of excess chemical potential in both initial and transition states for zeolites H-BEA, along with findings from HMFI, provides a basis to generalize and predict rates for hydronium-ion-catalyzed dehydration reactions in Brønsted zeolites.
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