Joseph W. Bennett, Jennifer L. Bjorklund, Tori Z. Forbes, Sara E. Mason

The interactions between aqueous aluminum (Al) nanoclusters and ions in solution influence the reactivity of nanomaterials in natural waters and are crucial to the targeted syntheses of aluminum oxides. To contribute to the fundamental understanding of how both anion and Al-nanocluster properties affect the interactions, we carry out systematic modeling studies that employ density functional theory calculations embedded in a continuum solvent model. Energetic and electronic structure analysis is applied toward delineating the interactions of a range of probe adsorbate anions with Al nanoclusters to elucidate how small molecules may react with naturally occurring nanomaterials. The study spans seven small molecules on three model Al nanoclusters. Using this ion set, we correlate the size, shape, and formal charge of the adsorbate to the trends in adsorption energies. A key finding is that the collective effects of exposed oxygen functional groups, i.e., the distribution of functional groups, dictates the electrostatic potential of the nanocluster surface, which, in turn, controls trends in anion adsorption. The computed adsorption and deprotonation trends are correlated to known synthetic routes of Al-nanocluster formation and subsequent crystallization to give insight into the potential optimization of synthetic conditions.