title: Electric double layer at metal oxide surfaces: static properties of the cassiterite-water interface.
abstract: The structure of water at the (110) surface of cassiterite (alpha-SnO2) at ambient conditions was studied by means of molecular dynamics simulations and X-ray crystal truncation rod experiments and interpreted with the help of the revised MUSIC model of surface protonation. The interactions of the metal oxide in the simulations were described by a recently developed classical force field based on the SPC/E model of water. Two extreme cases of completely hydroxylated and nonhydroxylated surfaces were considered along with a mixed surface with 50% dissociation. To study the dependence of the surface properties on pH, neutral and negatively charged variants of the surfaces were constructed. Axial and lateral density distributions of water for different types of surfaces were compared to each other and to experimental axial density distributions found by X-ray experiments. Although significant differences were found between the structures of the studied interfaces, the axial distances between Sn and O atoms are very similar and therefore could not be clearly distinguished by the diffraction technique. The explanation of structures observed in the density distributions was provided by a detailed analysis of hydrogen bonding in the interfacial region. It revealed qualitatively different hydrating patterns formed at neutral hydroxylated and nonhydroxylated surfaces and suggested a preference for the dissociative adsorption of water. At negatively charged surfaces, however, the situation can be reversed by the electric field stabilizing a hydrogen bond network similar to that found at the neutral nonhydroxylated surface. Comparison with previously studied rutile (alpha-TiO2) surfaces provided insight into the differences between the hydration of these two metal oxides, and an important role was ascribed to their different lattice parameters. A link to macroscopic properties was provided by the revised MUSIC surface protonation model. Explicit use of the Sn-O bond lengths based on ab initio calculations and H-bond configurations as inputs led to the prediction of a pH of zero net-proton induced surface charge (pHpzc) that agrees very well with those determined experimentally (about 4.4 at 298 K).
authors: Department of Chemical Engineering, Vanderbilt University, Nashville, Tennessee 37235-1604, USA. lukas.vlcek@vanderbilt.edu
authors: Lukas
authors: L
authors: Vlcek
authors: Zhan
authors: Z
authors: Zhang
authors: Mike L
authors: ML
authors: Machesky
authors: Paul
authors: P
authors: Fenter
authors: Jorgen
authors: J
authors: Rosenqvist
authors: David J
authors: DJ
authors: Wesolowski
authors: Larry M
authors: LM
authors: Anovitz
authors: Milan
authors: M
authors: Predota
authors: Peter T
authors: PT
authors: Cummings
mesh_terms: D006863:Hydrogen-Ion Concentration; D008567:Membranes, Artificial; D008958:Models, Molecular; D012542:Scattering, Radiation; D055672:Static Electricity; D013499:Surface Properties; D017971:Tin Compounds / Q000737:chemistry*; D014867:Water / Q000737:chemistry; D014965:X-Rays
chemical_list: D008567:Membranes, Artificial; D017971:Tin Compounds; D014867:Water; C045358:stannic oxide