Red-Shifted Absorptions of Cation-Defective and Surface-Functionalized Anatase with Enhanced Photoelectrochemical...

Manipulating the atomic structure of semiconductors is a fine way to tune their properties. The rationalization of their modified properties is, however, particularly challenging as defects locally disrupt the long-range structural ordering, and a deeper effort is required to fully describe their structure. In this work, we investigated the photoelectrochemical properties of an anatase-type structure featuring a high content of titanium vacancies stabilized by dual-oxide substitution by fluoride and hydroxide anions. Such atomic modification induces a slight red-shift band gap energy of 0.08 eV as compared to pure TiO₂, which was assigned to changes in titanium-anion ionocovalent bonding. Under illumination, electron paramagnetic resonance spectroscopy revealed the formation of Ti^III and O₂ ^- radicals which were not detected in defect-free TiO₂. Consequently, the modified anatase shows higher ability to oxidize water with lower electron-hole recombination rate. To further increase the photoelectrochemical properties, we subsequently modified the compound by a surface functionalization with N-methyl-2-pyrrolidone (NMP). This treatment further modifies the chemical composition, which results in a red shift of the band gap energy to 3.03 eV. Moreover, the interaction of the NMP electron-donating molecules with the surface induces an absorption band in the visible region with an estimated band gap energy of 2.25-2.50 eV. Under illumination, the resulting core-shell structure produces a high concentration of reduced Ti^III and O₂ ^-, suggesting an effective charge carrier separation which is confirmed by high photoelectrochemical properties. This work provides new opportunities to better understand the structural features that affect the photogenerated charge carriers.