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