Transitions in Al Coordination during Gibbsite Crystallization Using High-Field 27Al and 23Na MAS NMR Spectroscopy

Mechanisms of nucleation and growth of Al hydroxides such as gibbsite from aqueous solution, particularly in highly alkaline conditions, remain poorly understood. In this work, quantitative 27Al and 23Na MAS NMR experiments were conducted on solid samples extracted from the crystallization of gibbsite from an amorphous aluminum hydroxide gel precursor. The use of a high magnetic field and a moderate sample spinning rate of 20 kHz allowed transitional tetrahedral (AlT) and pentahedral (AlP) aluminum species to be observed along with the octahedral aluminum (AlO) that dominates the gibbsite product. Low-coordinated Al species could be detected at concentrations as low as 0.1% of the total Al sites. The following results have been established: (a) AlT and AlP coexist on the surface of growing gibbsites even with a combined percentage over the total Al sites of less than 1%. (b) Different synthesis methods generate gibbsite with varying amounts of low-coordinated Al. (c) The amorphous gel precursor contains a...