Boron removal and reinsertion studies in B-10-B-11 exchanged HAMS-1B (H-[B]-ZSM-5) borosilicate molecular sieves using solid-state NMR
authors Hough, A; Routh, AF; Clarke, SM; Wiper, PV; Amelse, JA; Mafra, L
nationality International
author keywords Borosilicate MFI zeolite; Industrial heterogeneous catalysis; Boron exchange; Framework and non-framework boron; B-11 MAS NMR; Solid-state NMR spectroscopy
abstract 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-/twodimensional B-11 solid-state NMR (SSNMR) spectroscopy. Uncalcined HAMS-1B shows only tetrahedral boron. However, three boron species are observed in B-11 SSNMR spectra of as-prepared and then calcined HAMS-1B: tetrahedral framework boron (B-[4](fr)), trigonal framework boron (B-[3](fr)), and non-framework trigonal boron (B-[3](NF)). 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 B-11 SSNMR on a series of B-10-B-11 exchanged borosilicate zeolites. We found that when boron is reinserted it enters at higher concentrations (similar to 40% more) as tetrahedral boron, not trigonal boron, thus reversing partial hydrolysis and removal during calcination. (C) 2015 Elsevier Inc. All rights reserved.
issn 0021-9517
year published 2016
volume 334
beginning page 14
ending page 22
digital object identifier (doi) 10.1016/j.jcat.2015.11.006
web of science category Chemistry, Physical; Engineering, Chemical
subject category Chemistry; Engineering
unique article identifier WOS:000369458100002
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