Crystal Growth and Design p. 4968 - 4974 (2016)
Update date:2022-08-16
Topics:
Mizuno, Kosuke
Mura, Takuto
Uchida, Sayaka
Two kinds of polymorphs of all-inorganic ionic crystals were obtained by the combination of oppositely charged molecular ions (macroions) with Td symmetry, Keggin-type polyaluminum hydroxide [?-Al13O4(OH)24(H2O)12]7+ (Al13) and polyoxometalates (POMs) [α-CoW12O40]6- (POM6), [α-1,2,3-SiVV3W9O40]7- (POM7), or [α-1,2,3-SiVIVVV2W9O40]8- (POM8) in aqueous solutions. The needle-type crystals were grown by dissolution-recrystallization of the precipitates, which formed immediately by combining Al13 and POMs. On the other hand, the plate-type crystals were grown by adding inorganic salts (e.g., NaCl) into the aqueous solution containing the needle-type crystals: Dissolution of the needle-type crystals occurred followed by precipitation of the plate-type crystals, which is the more insoluble and stable polymorph with larger numbers of hydrogen bonds between the constituent ions. The plate-type crystals possess one-dimensional channels with large apertures (ca. 12 ? × 6 ?) and showed high activities as heterogeneous solid acid catalysts in pinacol rearrangement.
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