Approaching enzymatic catalysis with zeolites or how to select one reaction mechanism competing with others

• Published in: Nature communications Vol. 14; no. 1; p. 2878
• Main Authors: Ferri, Pau, Li, Chengeng, Schwalbe-Koda, Daniel, Xie, Mingrou, Moliner, Manuel, Gómez-Bombarelli, Rafael, Boronat, Mercedes, Corma, Avelino
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 19.05.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 639/638/77/885; 639/638/77/887; 639/638/898; Aromatic compounds; Catalysis; Catalysts; Computer applications; Disproportionation; Enzymes; Humanities and Social Sciences; Intermediates; Methodology; multidisciplinary; Reaction intermediates; Reaction mechanisms; Science; Science (multidisciplinary); Transalkylation; Zeolites
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-38544-z

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. Approaching the level of molecular recognition of enzymes with solid catalysts is a challenging goal. Here, the authors present a computational methodology that guides the selection of the most adequate zeolite frameworks for target reactions.