Approaching the level of molecular recognition of enzymes with solid catalysts is a challenging goal, achieved in this work for the competing transalkylation and disproportionation of diethylbenzene catalyzed by acid zeolites. The key diaryl intermediates for the two competing reactions only differ in the number of ethyl substituents in the aromatic rings, and therefore finding a selective zeolite able to recognize this subtle difference requires an accurate balance of the stabilization of reaction intermediates and transition states inside the zeolite microporous voids. In this work we present a computational methodology that, by combining a fast high-throughput screeening of all zeolite structures able to stabilize the key intermediates with a more computationally demanding mechanistic study only on the most promising candidates, guides the selection of the zeolite structures to be synthesized. The methodology presented is validated experimentally and allows to go beyond the conventional criteria of zeolite shape-selectivity.

用固体催化剂接近酶的分子识别水平是一个具有挑战性的目标，在这项工作中实现了酸性沸石催化的二乙苯的竞争性烷基转移和歧化。两个竞争反应的关键二芳基中间体仅在芳环中乙基取代基的数量上有所不同，因此找到能够识别这种细微差异的选择性沸石需要准确平衡反应中间体的稳定性和沸石内部的过渡态微孔隙。在这项工作中，我们提出了一种计算方法，通过将能够稳定关键中间体的所有沸石结构的快速高通量筛选与仅对最有希望的候选物进行的计算要求更高的机理研究相结合，指导选择要合成的沸石结构。所提出的方法经过实验验证，并允许超越沸石形状选择性的传统标准。