Internalization of Foreign Ions into Meta-stable Lattices:a Case Study of Transition-metal-doped Brookite

The connections between the building units of meta-stable lattice were generally considered to be easily disturbed during the doping process, causing serious hindrances blocking the development of functional doped materials. In this work, the synthesis of doped brookite, a typical meta-stable phase of TiO2, has been explored novelly by in-situ adding of cations of VIIIB and IB,IIB elements in the 3rd period（Fe, Co, Ni, Cu, Zn） during the urea-lactate aided low-basicity hydrothermal process. The results showed that only Cu-doped brookite could be successfully synthesized with trace amount of copper intensively internalized into the brookite lattice, while the other dopants lead to the formation of anatase TiO2. Extensive characterizations indicated a two-step doping process, where copper ions were firstly dispersed in an amorphous layer on the lattice surface and then they were internalized into brookite lattice. Cu-doped brookite exhibited significantly enhanced photocatalytic activity in the phenol degradation under visible light compared to bare brookite. The enhancement of catalytic performance was assigned to the impurity band gap and the reduction of charge carriers’ recombination introduced by the internalization of Cu ions. The investigation reported herein contributes to the understanding of complex ion-doping effects on the structures of meta-stable materials, and provides hints for obtaining other functional doped materials.