title: Effect of Polar Environments on the Aluminum Oxide Shell Surrounding Aluminum Particles: Simulations of Surface Hydroxyl Bonding and Charge.
abstract: Density functional theory (DFT) calculations were performed to understand molecular variations on an alumina surface due to exposure to a polar environment. The analysis has strong implications for the reactivity of aluminum (Al) particles passivated by an alumina shell. Recent studies have shown a link between the carrier fluid used for Al powder intermixing and the reactivity of Al with fluorine containing reactive mixtures. Specifically, flame speeds show a threefold increase when polar liquids are used to intermix aluminum and fluoropolymer powder mixtures. It was hypothesized that the alumina lattice structure could be transformed due to hydrogen bonding forces exerted by the environment that induce modified bond distances and charges and influence reactivity. In this study, the alumina surface was analyzed using DFT calculations and model clusters as isolated systems embedded in polar environments (acetone and water). The conductor-like screening model (COSMO) was used to mimic environmental effects on the alumina surface. Five defect models for specific active -OH sites were investigated in terms of structures and vibrational -OH stretching frequencies. The observed changes of the surface OH sites invoked by the polar environment were compared to the bare surface. The calculations revealed a strong connection between the impact of carrier fluid polarity on the hydrogen bonding forces between the surface OH sites and surrounding species. Changes were observed in the OH characteristic properties such as OH distances (increase), atomic charges (increase), and OH stretching frequencies (decrease); these consequently improve OH surface reactivity. The difference between medium (acetone) and strong (water) polar environments was minimal in the COSMO approximation.
authors.forename: Richa
authors.initials: R
authors.lastname: Padhye
authors.forename: Adelia J A
authors.initials: AJ
authors.lastname: Aquino
authors.affiliation: Institute for Soil Research, University of Natural Resources and Life Sciences , Peter-Jordan-Strasse 82, A-1190 Vienna, Austria.
authors.forename: Daniel
authors.initials: D
authors.lastname: Tunega
authors.forename: Michelle L
authors.initials: ML
authors.lastname: Pantoya
keywords: DFT calculations; alumina catalysis; aluminum combustion; fluoropolymer reactions; implicit solvent model; modified alumina structures