Dry-gel synthesis of Ti-beta for epoxidation of unsaturated fatty acid methyl esters (FAMEs)

Abstract

The Ti-beta was synthesized via a dry-gel conversion approach with the direct incorporation of titanium from titano-aluminosilicate nanobeads (Ti-SiAl-NB). At first, the Ti-SiAl-NB was prepared and employed as the precursor for zeolite crystallization. Powder XRD (PXRD) patterns confirm the amorphous nature of the nanobeads. These Ti-SiAl-NB precursors were subsequently converted to the Ti-beta zeolite via the dry-gel conversion approach. Structural characterization using PXRD, high-resolution TEM, and selected area electron diffraction (SAED) confirmed the formation of a beta zeolite framework, with dominant lattice planes indexed to (101) and (302). UV-vis DRS indicated that Ti existed as a tetrahedrally coordinated (TiIV) and non-framework Ti. Unfortunately, the as-synthesized Ti-beta exhibited a low catalytic activity in methyl oleate (MO) epoxidation, which is attributed to the prevalence of closed site TiIV [Ti(OSi)4] species that restrict substrate accessibility to active sites. To address this limitation, a post-synthetic treatment involving framework etching was applied to generate open site TiIV [Ti(OSi)3OH] species. As a result, MO conversion increased by approximately 2.73-fold, with epoxide selectivity up to 70%. Catalyst stability tests demonstrated sustained MO conversion of 65–72% and epoxide selectivity above 65% over several consecutive catalytic cycles. This work highlights a sustainable catalyst design strategy that combines the dry-gel conversion process with mild post-treatment to enhance active site accessibility and catalytic performance in the epoxidation of bulky molecules.