Dynamic Evolution of Aluminum Coordination Environments in Mordenite Zeolite and Their Role in the Dimethyl Ether (DME) Carbonylation Reaction

Abstract Part of tetrahedral framework aluminum in a protonic mordenite (HMOR) will convert geometry to distorted tetrahedral and octahedral coordination. High‐field 27 Al NMR data show that more framework Al atoms at T 3 and T 4 sites change geometry to nonframework structures than others. These nonframework Al species preferentially reside in the side pockets, which will decrease the accessibility of acid sites in the 8‐membered ring (MR) channel, impairing the dimethyl ether (DME) carbonylation reaction. The arisen octahedrally coordinated Al species are framework‐associated, which can be reverted into the zeolite framework. Herein, we find that a facile treatment with pyridine could force the octahedral coordination Al back into a tetrahedral environment, which could increase the number of available active sites and enhance the diffusion of DME, thus improving the reactivity (4 times) of the DME carbonylation reaction and prolonging the lifetime of catalysts.