Controlling the Morphology and Titanium Coordination States of TS-1 Zeolites by Crystal Growth Modifier

Abstract

Developing an effective strategy to synthesize perfect titanosilicate TS-1 zeolite crystals with desirable morphologies, enriched isolated framework Ti species, and thus enhanced catalytic oxidation properties is a pervasive challenge in zeolite crystal engineering. We here used an amino acid l-carnitine as a crystal growth modifier and ethanol as a cosolvent to regulate the morphologies and the Ti coordination states of TS-1 zeolites. During the hydrothermal crystallization process, the introduced l-carnitine can not only tailor the anisotropic growth rates of zeolite crystals but also induce the formation of uniformly distributed framework Ti species through building a suitable chemical interaction with the Ti precursor species. Condition optimizations could afford the generation of perfect hexagonal plate TS-1 crystals and elongated platelet TS-1 crystals enriched in tetrahedral framework Ti sites (TiO₄) or mononuclear octahedrally coordinated Ti species (TiO₆). Both samples showed significant improvement in catalytic activity for the H₂O₂-mediated epoxidation of alkenes. In particular, the elongated platelet TS-1 enriched in "TiO₆" species afforded the highest activity in 1-hexene epoxidation, with a turnover frequency (TOF) of up to 131 h^-1, which is approximately twice as high as that of the conventional TS-1 zeolite (TOF: 65 h^-1) and even higher than those of the literature-reported TiO₆-containting TS-1 catalysts derived from the hydrothermal post-treatment of TS-1 zeolites. This work demonstrates that the morphologies and the titanium coordination states of TS-1 zeolites can be effectively tuned by directly introducing suitable crystal growth modifiers, thus providing new opportunities for developing highly efficient titanosilicate zeolite catalysts for important catalytic applications.