Properties of hydrated TiO2 and SiO2 nanoclusters: dependence on size, temperature and water vapour pressure

Abstract

Nanoscale titania (TiO₂) and silica (SiO₂) are massively produced technologically important nanomaterials used in a wide range of technological applications where nano-titania is the active component (e.g. water splitting, pollution remediation, self-cleaning coatings). Generally, these applications entail contact with water and a degree of hydration of these nano-oxides. Although the hydration of nano-silica has been fairly well studied, the corresponding level of microscopic understanding for nano-titania is severely lacking. Here, using accurate electronic structure calculations we perform a detailed and comprehensive study of the hydration of titania nanoclusters. Firstly, using global optimisation, we establish the most energetically stable structures of a set of (TiO₂)_M(H₂O)_N nanoclusters with sizes ranging through M = 4–16 and with N/M ratios of ≤ 1.0. Using this extensive dataset we investigate how the structures, energy gaps, and thermodynamic stabilities of these species depend on size, temperature and water vapour pressure. To provide a broader chemical context for our study we also provide this full set of data for the respective set of (SiO₂)_M(H₂O)_N nanoclusters which we use to compare and contrast their properties with those of nano-titania. Our broad systematic study thus provides a comparative and foundational reference study for a thorough understanding of how hydration affects the structure, energetics and properties of both nano-SiO₂ and nano-TiO₂.