Role of 12-Ring Channels of Mordenite in DME Carbonylation Investigated by Solid-State NMR

In this work, we have studied the role of the 12-ring channel of mordenite in DME carbonylation. Upon modification with pyridine, the catalytic lifetime of mordenite in DME carbonylation was prolonged dramatically although its activity decreased slightly and the induction period increased. 1H MAS NMR and PFG-NMR results demonstrated that the acid quantity decreased after pyridine was adsorbed, and the self-diffusion coefficient of CH4 decreased with the increase in pyridine quantity in the 12-ring channel. 129Xe NMR results reveal that Xe atoms are preferentially adsorbed in an 8-ring side pocket at low pressure; xenon can enter the 8-ring side pocket at high temperature through the 12-ring channels only. From these results, the function of the 12-ring with respect to the reaction rate is explored and a transfer path of reactants/products is proposed.