The organization of aluminium atoms in zeolites affects their catalytic properties. Here we demonstrate that the aluminium distribution is a key parameter controlling the reaction pathway of acid catalysed reactions over ZSM-5 zeolites. We study ethanol transformation over two ZSM-5 samples with similar Si/Al ratios of ~15, and with aluminium atoms located mainly at the channel intersections but differently distributed in the framework. One of the samples contains mostly isolated aluminium atoms while the other has a large fraction of two aluminium atoms located in one ring. The FT-IR time-resolved operando study, supported by catalytic results, reveals that the reaction pathway in ethanol transformation over ZSM-5 is controlled by the proximity of aluminium atoms in the framework. ZSM-5 containing mostly isolated Al atoms transforms ethanol in the associative pathway, and conversely ZSM-5 containing a dominating fraction of two aluminium atoms in one ring transforms ethanol in the dissociative pathway.

Faculty of Chemistry Jagiellonian University in Kraków Gronostajowa 2 30 387 Kraków Poland

J Heyrovský Institute of Physical Chemistry of the CAS Dolejškova 2155 3 182 23 Prague 8 Czech Republic

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