Hydrothermal Modification of TS-1 Zeolites with Organic Amines and Salts to Construct Highly Selective Catalysts for Cyclopentene Epoxidation

Abstract

Developing efficient heterogeneous catalysts for cyclic olefins epoxidation is highly attractive for meeting the growing need for various cyclic epoxides. Herein, hierarchical TS-1 zeolite with relatively abundant mesopores and less amount of surface hydroxyl groups was obtained by hydrothermal modification of an as-synthesized TS-1 zeolite with a mixed solution of ammonia, tetrapropylammonium bromide (TPABr) and KCl. The post-modified TS-1 zeolite exhibited much higher catalytic activity (52% conversion) and epoxide selectivity (98%) for the epoxidation of cyclopentene than the conventional TS-1 zeolites. The excellent catalytic activity of the hierarchical TS-1 could be mainly assigned to the enhancement of the mass transport ability and the accessibility of the active Ti species, while the improvement of epoxidation selectivity may be mainly related to the introduction of a certain amount of K+ that can effectively modulate the coordination environment of Ti species as well as the polarity of the zeolite. This work demonstrated that a highly active and selective catalyst for the H2O2-mediated cyclopentene epoxidation could be obtained by concurrently generating mesopore and extinguishing the unfavorable defective hydroxyl groups through the simple hydrothermal treatment of the conventional TS-1 zeolite with a mixed base/salt solution.