Evaluating Water Reactivity at Silica Surfaces Using Reactive Potentials

TS Mahadevan and JC Du, JOURNAL OF PHYSICAL CHEMISTRY C, 122, 9875-9885 (2018).

DOI: 10.1021/acs.jpcc.7b12653

Understanding the interactions between amorphous silica surfaces and water provides insight into material degradation of silicate glasses and minerals in aqueous environment. Molecular dynamics (MD) simulations of water and nanometer sized silica structures were used in this work to evaluate the reactivity of flat silica surface and surfaces with curvature. We compared two dissociable water/silica potentials, namely the Reactive Force Field (ReaxFF) and the Mahadevan-Garofalini water/silica force field (MGFF) that have been in development over the past decade, to study their performance in simulating bulk water as well as silica-water interactions. Significant differences in the properties of bulk water as well as surface interactions were observed between the two types of potentials, as well in the same potential type with two parametrizations for ReaxFF, suggesting a need for improvement of the existing water/silica ReaxFF potentials. Our simulation results show that a majority of the silanols were formed by reactions between water and strained siloxane bonds that mainly exist on the surface of amorphous silica, within a few nanoseconds of the simulation time scale, in agreement with previous studies. Effect of surface curvature on the reactivity with water was investigated. Our results indicate that defect concentration at the surface bears a strong correlation to the concentration of silanols (Si-OH) that eventually form. We observe undercoordinated Si's at the surface that are attacked by water before the hydrolysis reaction of the siloxane bonds and demonstrate possible mechanisms of water reacting with these undercoordinated Si's. We also find that the method of generating surfaces in simulation determines the defect concentration and hence influences the reactivity of the amorphous silica surface.

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