Roles of Hydroxyl Groups during Side-Chain Alkylation of Toluene with Methanol over Zeolite Na-Y： A Density Functional Theory Study

The side-chain alkylation of toluene with methanol over alkali-cation-containing zeolite Y is an important reaction for industrial production of styrene,but the exact mechanism of this reaction is still unclear.The most accepted opinion is that the Lewis acid-base sites in zeolite Y activate the transformation from methanol to formaldehyde,the side-chain alkylation of toluene with formaldehyde,and the formation of 2-phenylethanol and styrene afterwards.In this study,we investigate the roles of various types of hydroxyl groups that could possibly exist in zeolite Na-Y during this reaction,including the Br6nsted acid sites and the terminal Al-OH and Si-OH groups,respectively.Through density functional theory （DFT） calculations,we find that the Brtnsted acid sites in Na-Y may catalyze the ring alkylation of toluene and be responsible for the formation of xylene,a side product discovered in experiments.More importantly,we find,for the first time,a new reaction pathway from 2-phenylethanol to styrene over various types of hydroxyl groups in Na-Y,which is kinetically more favorable than the conventional pathway.According to our calculation results,the most possible mechanism for this styrene production process may involve reactions over both the Lewis acid-base sites and the hydroxyl groups in Na-Y.