Protective dissolution: generating secondary pores in zeolite by mechanochemical reaction

Introduction of meso-/macropores into the intrinsic microporous framework of zeolites has raised substantial interest in catalytic reactions with bulky reactants. Herein, we report the formation of secondary meso-/macropores in Silicalite-1 zeolite by a solvent-free mechanochemical grinding process. The strategy allows the preservation of high crystallinity and microporosity of the pristine zeolite, and the generation of mesopores at room temperature and marcopores at higher temperatures. The roles of the tetrapropylammonium bromide (TPABr) and ammonium fluoride (NH₄F) have been proposed and demonstrated. A protective layer is formed by TPA⁺ ions bonded with the surficial defects to shield the outer surface from the direct attack by F^-. Instead, F^- diffuses into the micropore system in a local aqueous environment within zeolite formed by the mechanochemical reaction. As a result, freely diffused F^- selectively dissolves zones with structural defects to form secondary pores inside the zeolite. Moreover, this strategy proves highly effective in encapsulation of nanoparticles (Pt, Co) in the meso-/macropores of Silicalite-1 zeolite, forming a yolk-shell composite catalyst for potential applications.