Three-phase junction for modulating electron–hole migration in anatase–rutile photocatalysts† †Electronic supplementary information (ESI) available: Optimized structures (XYZ coordinates) for pure phase and biphase crystals; other structure models for phase junction. See DOI: 10.1039/c5sc00621j

The heterophase solid–solid junction as an important type of structure unit has wide applications for its special mechanics and electronic properties. Here we present a first three-phase atomic model for the anatase–rutile TiO2 heterophase junction and determine its optical and electronic properties, which leads to resolution of the long-standing puzzles on the enhanced photocatalytic activity of anatase– rutile photocatalysts. By using a set of novel theoretical methods, including crystal phase transition pathway sampling, interfacial strain analysis and first principles thermodynamics evaluation of holes and electrons, we identify an unusual structurally ordered three-phase junction, a layer-by-layer “T-shaped” anatase/TiO2-II/rutile junction, for linking anatase with rutile. The intermediate TiO2-II phase, although predicted to be only a few atomic layers thick in contact with anatase, is critical to alleviate the interfacial strain and to modulate photoactivity. We demonstrate that the three-phase junction acts as a single-way valve allowing the photogenerated hole transfer from anatase to rutile but frustrating the photoelectron flow in the opposite direction, which otherwise cannot be achieved by an anatase–rutile direct junction. This new model clarifies the roles of anatase, rutile and the phase junction in achieving high photoactivity synergistically and provides the theoretical basis for the design of better photocatalysts by exploiting multi-phase junctions.