DOE OSTI2017
Al-rich aluminum borates were prepared by different synthesis routes using various Al/B ratios, characterized by diffraction methods, spectroscopy and prompt gamma activation analysis. The {sup 11}B NMR data show a small amount of BO{sub 4} species in all samples. The chemical analysis indicates a trend in the Al/B ratio instead of a fixed composition. Both methods indicate a solid solution Al{sub 5−x}B{sub 1+x}O{sub 9} where Al is substituted by B in the range of 1–3%. The structure of B-rich Al{sub 4}B{sub 2}O{sub 9} (C2/m, a=1488 pm, b=553 pm, c=1502 pm, ß=90.6°), was re-investigated by electron diffraction methods, showing that structural details vary within a crystallite. In most of the domains the atoms are orderly distributed, showing no signal for the postulated channel oxygen atom O5. The absence of O5 is supported by density functional theory calculations. Other domains show a probable disordered configuration of O5 and O10, indicated by diffuse scattering along the b direction. - Graphical abstract: Projections of three-dimensional electron diffraction space of Al{sub 4}B{sub 2}O{sub 9} along the main directions. - Highlights: • The crystal structure of Al{sub 4}B{sub 2}O{sub 9} was re-evaluated. • Structural details vary among different crystals and inside Al{sub 4}B{sub 2}O{sub 9} crystallites. • Diffuse scattering indicate a probable disordered configuration of O5 and O10. • A solid solution series for Al{sub 5−x}B{sub x}O{sub 9} is indicated by PGAA and NMR spectroscopy. • The presence of BO{sub 4} groups is confirmed by {sup 11}B MAS NMR spectroscopy for Al{sub 5−x}B{sub 1+x}O{sub 9}.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗