Anionic Dopant Delocalization through p-Band Modulation to Endow Metal Oxides with Enhanced Visible-Light Photoactivity

An N-doped TiO₂ model reveals a conceptually different mechanism for activating the N dopant based on delocalized orbital hybridization through O vacancy incorporation. Synchrotron-based X-ray absorption spectroscopy, time-resolved fluorescence, and DFT studies revealed that O vacancy incorporation can effectively stimulate the delocalization of N impurity states through p-band orbital modulation, which leads to a significant enhancement in photocarrier lifetime. Consequently, this effect also results in a remarkable increase in the incident photon-to-electron conversion efficiency in the range of 400-550 nm compared to that of conventional N-incorporated TiO₂ (15 % versus 1 % at 450 nm). This work reveals the fundamental necessity of orbital modulation in the band engineering of metal oxides for driving solar water splitting and beyond.