Insight into the mechanism of the solvolysis of propylene oxide over titanium silicalite-1: A theoretical study

In order to probe into the mechanism of solvolysis (alcoholysis/hydrolysis) of propylene oxide (PO), the formation of propylene glycol (PG), 1-methoxy-2-propanol (PPM) and 2-methoxy-1-propanol (SPM) over the TS-1 catalyst with tetrahedral Ti and Ti/defect sites was systematically discussed using an embedded quantum mechanical/molecular mechanics (QM/MM) approach. The results showed that the activity of PO solvolysis is closely related to the ring-opening ability of active substances, and the ring-opening ability is in the following order: Si-O(H)-Ti > Ti-OH > 5MR Ti-OOH > Ti-OCH3 (tetrahedral Ti site); 3MR Ti-OOH > Ti-OH > 5MR Ti-OOH > Ti-OCH3 (Ti/defect site). At the tetrahedral site, the concerted mechanism is the dominant pathway for PO ring opening to form PPM, while a competitive relationship exists between stepwise and concerted mechanisms to form PG and SPM. Si-O(H)-Ti exhibits excellent PO ring-opening activity because of its strong Brønsted acidity, but it is difficult to form. At the Ti/defect site, the stepwise mechanism via PO ring opening with 3MR Ti-OOH and then successive hydrolysis/alcoholysis to form product is the dominant pathway. The overall energy barrier of the optimal route is relatively lower as compared to the tetrahedral Ti site. This work opens up a new path for providing more information on the detailed mechanism in the solvolysis of PO over the TS-1 catalyst from a theoretical point of view.