Synergistic Design of Anatase–Rutile TiO2 Nanostructured Heterophase Junctions toward Efficient Photoelectrochemical Water Oxidation

Synergistically designing porous nanostructures and appropriate band alignment for TiO2 heterophase junctions is key to efficient charge transfer, which is crucial in enhancing photoelectrochemical (PEC) water splitting for hydrogen production. Here, we investigate the efficiency of PEC water oxidation in anatase–rutile TiO2 nanostructured heterophase junctions that present the type-II band alignment. We specifically prove the importance of a phase alignment in heterophase junction for effective charge separation. The TiO2 heterophase junctions were prepared by transferring TiO2 nanotube (TNT) arrays onto FTO substrate with the help of a TiO2 nanoparticle (TNP) glue layer. The PEC characterization reveals that the rutile (R)-TNT/anatase (A)-TNP heterophase junction has a higher photocurrent density than those of A-TNT/R-TNP junction and anatase or rutile single phase, corresponding to twofold enhanced efficiency. This type-II band alignment of R-TNT/A-TNP for water oxidation, in which photogenerated electrons (holes) will flow from rutile (anatase) to anatase (rutile), enables to facilitate efficient electron-hole separation as well as lower the effective bandgap of heterophase junctions. This work provides insight into the functional role of heterophase junction for boosting the PEC performances of TiO2 nanostructures.