Computational study on the structural and surface properties of amorphous hydroxylated TiO2 spherical nanoparticles

Monte Carlo simulations were carried out on amorphous titanium dioxide (TiO2) for both bulk and hydroxylated nanoparticles with particle sizes ranging from 1 to 10 nm. The potential developed by the Matsui and Akaogi (MA) was used to model the interatomic interactions of TiO2 in both cases (bulk and nanoparticles). Besides, Angular and Morse potentials proposed by the Tether, Cormack, Du et. al. (TCD) were introduced to model the interactions of hydroxyl groups on the TiO2 surfaces, i.e., the Ti-O-H groups with an experimental and theoretical angles of 125 o . The bulk system was developed using periodic boundary conditions. The TiO2 nanoparticles were extracted by applying a spherical cut section in the bulk TiO2 melt structure to obtain the required size. Free valences on the nanoparticle surfaces were saturated via additional hydroxyl groups and then quenched to 300 K under free boundary conditions. The bulk and surface properties of the nanoparticles were calculated at 300 K and zero pressure and characterized via radial distribution functions, bond angle distributions, bond distances, coordination numbers, OH group concentrations and radial density profiles. In addition, to understand the difference in properties of amorphous hydroxylated TiO2 nanoparticles and bulk amorphous TiO2, a comparative study was done at the same thermodynamic conditions. The study shows that the bulk properties of amorphous hydroxylated TiO2 nanoparticles are strongly size-dependent and different from those of the bulk TiO2. As expected, increasing the particle size leads to an approach of the particle’s bulk properties to the bulk properties of the (quasi) infinite system. The size effects show that decreasing the particle size results in increasing the surface effects and surface OH group concentrations. Accordingly, small-sized TiO2 nanoparticles have higher surface OH group concentrations and larger surface effects than large-sized TiO2 nanoparticles. Larger surface effects result significant changes in their bond angles, bond distances, and coordination numbers. The simulation results of the surface properties reveal that the surface titanium atoms in the TiO2 nanoparticles have the capability of accommodating up to 5 hydroxyl groups. The mean surface hydroxyl group density of the amorphous TiO2 spherical nanoparticles is estimated to be around 8.1/nm 2, which lies in the range of 8–16/nm 2, found by experimental and other simulation studies. Details of the modelling, simulations results and the study are presented in this paper.