Crystal properties without crystallinity? Influence of surface hydroxylation on the structure and properties of small TiO2 nanoparticles

Titania (TiO2) nanoparticles (NPs) are widely employed in applications that take advantage of their photochemical properties (e.g. pollutant degradation, photocatalysis). Here, we study the interrelation between crystallinity, surface hydroxylation and electronic structure in titania NPs with 1.4–2.3 nm diameters using all electron density functional theory-based calculations. We show how the distribution of local coordination environments of the atoms in thermally annealed quasi-spherical non-crystalline NPs converge to those in correspondingly sized faceted crystalline anatase NPs upon increasing hydroxylation. When highly hydroxylated, annealed NPs also possess electronic energy gaps with very similar energies and band edge orbital characters to those of the crystalline anatase NPs. We refer to the crystallite-mimicking non-crystalline annealed NPs as “crystalikes”. Small stable crystalike NPs could allow for photochemical applications of titania in the size range where crystalline anatase NPs tend to become thermodynamically unfavoured (