Hydration Structures on gamma-Alumina Surfaces With and Without Electrolytes Probed by Atomistic Molecular Dynamics Simulations

O Drecun and A Striolo and C Bernardini and M Sarwar, JOURNAL OF PHYSICAL CHEMISTRY B (2022).

DOI: 10.1021/acs.jpcb.2c06491

A wide range of systems, both engineered and natural, feature aqueous electrolyte solutions at interfaces. In this study, the structure and dynamics of water at the two prevalent crystallographic terminations of gamma alumina, 110 and 100, and the influence of salts -sodium chloride, ammonium acetate, barium acetate, and barium nitrate on such properties were investigated using equilibrium molecular dynamics simulations. The resulting interfacial phenomena were quantified from simulation trajectories via atomic density profiles, angle probability distributions, residence times, 2-D density distributions within the hydration layers, and hydrogen bond density profiles. Analysis and interpretation of the results are supported by simulation snapshots. Taken together, our results show stronger interaction and closer association of water with the 110 surface, compared to 100, while ion induced disruption of interfacial water structure was more prevalent at the 100 surface. For the latter, a stronger association of cations is observed, namely sodium and ammonium, and ion adsorption appears determined by their size. The differences in surface-water interactions between the two terminations are linked to their respective surface features and distributions of surface groups, with atomistic-scale roughness of the 110 surface promoting closer association of interfacial water. The results highlight the fundamental role of surface characteristics in determining surface-water interactions, and the resulting effects on ion-surface and ion-water interactions. Since the two terminations of gamma-alumina considered represent interfaces of significance to numerous industrial applications, the results provide insights relevant for catalyst preparation and adsorption-based water treatment, among other applications.

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