Searching for new TiO₂ crystal phases with better photoactivity

Using the recently developed stochastic surface walking global optimization method, this work explores the potential energy surface of TiO2 crystals aiming to search for likely phases with higher photocatalytic activity. Five new phases of TiO2 are identified and the lowest energy phase transition pathways connecting to the most abundant phases (rutile and anatase) are determined. Theory shows that a high-pressure phase, α-PbO2-like form (TiO2II) acts as the key intermediate in between rutile and anatase. The phase transition of anatase to rutile belongs to the diffusionless Martensitic phase transition, occurring through a set of habit planes, rutile(101)//TiO2II(001), and TiO2II(100)//anatase(112). With regard to the photocatalytic activity, three pure phases (#110, pyrite and fluorite) are found to possess the band gap narrower than rutile, but they are unstable at the low-pressure condition. Instead, a mixed anatase-TiO2II phase is found to have good stability and narrower band gap than both parent phases. Because of the phase separation, the mixed phase is also expected to improve the photocatalytic performance by reducing the probability of the electron-hole pair recombination.