Al NMR diffusometry of Al Keggin nanoclusters.

Although nanometer-sized aluminum hydroxide clusters (i.e., ϵ-Al , [Al O (OH) (H O) ] ) command a central role in aluminum ion speciation and transformations between minerals, measurement of their translational diffusion is often limited to indirect methods. Here, Al pulsed field gradient stimulated echo nuclear magnetic resonance (PFGSTE NMR) spectroscopy has been applied to the AlO core of the ϵ-Al cluster with complementary theoretical simulations of the diffusion coefficient and corresponding hydrodynamic radii from a boundary element-based calculation. The tetrahedral AlO center of the ϵ-Al cluster is symmetric and exhibits only weak quadrupolar coupling, which results in favorable T and T Al NMR relaxation coefficients for Al PFGSTE NMR studies. Stokes-Einstein relationship was used to relate the Al diffusion coefficient of the ϵ-Al cluster to the hydrodynamic radius for comparison with theoretical simulations, dynamic light scattering from literature, and previously published H PFGSTE NMR studies of chelated Keggin clusters. This first-of-its-kind observation proves that Al PFGSTE NMR diffusometry can probe symmetric Al environments in polynuclear clusters of greater molecular weight than previously considered.