Switching between classical/nonclassical crystallization pathways of TS-1 zeolite: implication on titanium distribution and catalysis

In the MFI zeolite crystallization process, the classical crystallization mechanism based upon the addition of silica species is often concomitant with the nonclassical route that is characteristic of the attachment of silica nanoparticle precursors. However, the factors that govern the preferences for each mechanism remain unclear. In this work, we present the impact of switching between these two crystallization pathways on the active sites and the resulting catalytic performance of the titanosilicate TS-1 zeolite. By controlling the self-assembled precursor structures in the early crystallization stage which are mediated by the Ti and H₂O in the reaction system, we could achieve the preferred modes of crystal growth of the TS-1 zeolite. We indicate that by directing the predominant crystallization path from the classical to the nonclassical route, it is possible to generate more stable bridging peroxo species upon reaction with hydrogen peroxide, as confirmed by ¹⁷O solid-state nuclear magnetic resonance spectroscopy, thus substantially increasing the catalytic performance of the resulting TS-1 for olefin epoxidation.