Influence of Silanol Defects of ZSM-5 Zeolites on Trioxane Synthesis from Formaldehyde

The silanol defects in ZSM-5 zeolite have been recognized as an important factor in catalytic activity. Here, ZSM-5 zeolites with different amounts of silanol defect sites were synthesized from synthetic gels containing fluoride medium and were applied as catalysts for trioxane synthesis. The results of XRD, SEM, NH 3 -TPD, Py-IR, OH-IR, 27 Al MAS NMR, 1 H MAS NMR, and TG indicated that all ZSM-5 zeolites showed similar crystal size, relative crystallinity, porosity, and the number of Brønsted acid sites. However, the silanol defects reduced obviously and the number of Lewis acid sites reduced correspondingly when a little NH 4 F was added in the synthesis gels and both of them decreased slightly with increase of F/Si ratio. Compared with ZSM-5 zeolite prepared in hydroxide medium, ZSM-5 zeolite prepared in fluoride medium displayed higher selectivity to trioxane and increased gradually with increase of F/Si ratio. Moreover, the lifetime of ZSM-5 zeolite prepared in fluoride medium was longer than that of prepared in hydroxide medium. Thus, ZSM-5 zeolite prepared in fluoride medium which contained the few silanol defects and low Lewis acid sites is an efficient catalyst for trioxane synthesis. Graphic Abstract