Rational Design of Isolated Tetrahedrally Coordinated Ti(IV) Sites in Zeolite Frameworks for Methyl Oleate Epoxidation.

Abstract

The rational design of isolated metals containing zeolites is crucial for the catalytic conversion of biomass-derived compounds. Herein, we explored the insertion behavior of the isomorphic substitution of Ti(IV) in different zeolite frameworks, including ZSM-35 (FER), ZSM-5, and BEA. The different aluminium topological densities of each zeolite framework lead to the creation of different degrees of vacant sites for hosting the tetrahedrally coordinated Ti(IV) active sites. These observations show the precise control of the degree of four-coordinated Ti(IV) sites in a zeolite framework, especially in BEA topology, by tuning the degree of unoccupied sites in the host zeolite structure via dealumination. Interestingly, the more vacancies in the host zeolite structure, the more isolated tetrahedrally coordinated Ti(IV) can be increased, eventually enhancing the catalytic performance in methyl oleate (MO) epoxidation for producing methyl-9,10-epoxystearate (EP). The engineered Ti-β exhibits outstanding performances in bulky MO epoxidation with the amount of produced EP per number of Ti sites up to 17.1±1.8 mol mol-1. This observation discloses an alternative strategy for optimizing catalyst efficiency in the rational design of the Ti-embedding zeolite catalyst, endeavoring to reach highly efficient catalytic performance.