Abstract
The recent observation of spectacular photocatalytic activity enhancements generated tremendous interest in the
synthesis, properties, and potential applications of black titania. Most black titania are core–shell structures
consisting of a perfect crystalline core surrounded by a defective surface shell. Because the properties are
attributed to the defective shell, it is particularly important, but very challenging, to obtain atomic structure
information of the core, the shell, and the core–shell relationship on a single particle level. While the role of
various synthesis approaches for producing black titania with different properties has been extensively reviewed,
this review focuses on understanding the structure–functionality relationship in black titania on a single particle
level. We start by introducing the crystal and electronic band structure of different TiO2 phases, followed by the
discussion of particle size effects, the origin of lattice distortions, and phase control by synthesis, and concluding
with the discussion of crystalline order formation and evolution creating the defective shell.
