Boron removal and reinsertion studies in 10 B– 11 B exchanged HAMS-1B (H-[B]-ZSM-5) borosilicate molecular sieves using solid-state NMR

Display Omitted * New atomic-level insight of boron removal and reinsertion mechanism into the H-[B]-ZSM-5 framework. * Boron reinsertion proved by 11 B solid-state NMR on 10 B- B exchanged borosilicate zeolites. * SSNMR identification of boron species at distinct hydration levels. * SSNMR identification of boric acid in H-[B]-ZSM-5. Novel atomic-level insight in boron removal and reinsertion into the framework of a HAMS-1B (H-[B]-ZSM-5) borosilicate molecular sieve was obtained by a combination of wet chemistry and one-/two-dimensional 11 B solid-state NMR (SSNMR) spectroscopy. Uncalcined HAMS-1B shows only tetrahedral boron. However, three boron species are observed in 11 B SSNMR spectra of as-prepared and then calcined HAMS-1B: tetrahedral framework boron ([4] Bfr), trigonal framework boron ([3] Bfr), and non-framework trigonal boron ([3] BNF). A picture has emerged as to the origins of these three species. Trigonal boron species are formed via hydrolysis by reaction with the water formed from water release and water formed by oxidation and removal of the template during calcination. The trigonal boron species are readily removed from the framework by slurrying in water or mild acid solutions. Tetrahedral boron remains at a concentration about equal to that in the calcined sieve not slurried, indicating that it is more difficult to remove. The extent of boron removal and reinsertion is pH dependent. We demonstrate that boron is removed to a greater extent at low pH and can be reinserted when pH is increased. Boron reinsertion into the framework is proven by 11 B SSNMR on a series of 10 B-11 B exchanged borosilicate zeolites. We found that when boron is reinserted it enters at higher concentrations (∼40% more) as tetrahedral boron, not trigonal boron, thus reversing partial hydrolysis and removal during calcination.