Ga3+ Incorporation into Al13 Keggin Polyoxometalates and the Formation of δ-(GaAl12)7+ and (Ga2.5Al28.5)19+ Polycations.

Inorganic Chemistry
Mohammad ShohelTori Z Forbes

Abstract

Keggin-type polyaluminum species (ε-Al13, δ-Al13, Al26, Al30, Al32) can form upon partial hydrolysis of Al3+-bearing solutions and are important species for water purification and contaminant transport. While the structural features for the major Al3+ polyaluminum species have been delineated, much less is known regarding heteroatom substitution and resultant structures other than the previously identified ε-GaAl127+ and ε-GeAl128+ cations. Single-atom substitution within polyaluminum species can change the surface reactivity within water treatment scenarios; thus, it is important to understand heteroatom incorporation within this system. The present work describes the synthesis and characterization of two novel Ga3+-substituted Keggin-type polyaluminum species. Na[GaO4Al12(OH)24(H2O)12](2,6-NDS)4(H2O)20.5 (δ-GaAl12) and [Ga2O8Al28.5Ga0.5(OH)58(H2O)27(SO4)2](SO4)4Cl7(H2O)8.5 (Ga2.5Al28.5) were crystallized from a thermally aged, partially hydrolyzed Ga3+/Al3+ solution. Structural refinement from single-crystal X-ray diffraction indicated fully occupied Ga3+ within tetrahedral site(s) of both isolated species. Partial substitution was observed for octahedral sites for the larger Ga2.5Al28.5 cluster. The chemical compositions of ...Continue Reading

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