Red anatase TiO₂ microspheres with exposed major {001} facets and boron-stabilized hydrogen-occupied oxygen vacancies...

In pursuit of efficient solar energy to chemical energy conversion through band engineering of wide-bandgap photocatalysts such as TiO₂, a compromise occurs between a narrow bandgap and high-redox-capacity photo-induced charge carriers, which impairs the potential advantages associated with the widened absorption range. The key to this compromise is an integrative modifier that can simultaneously modulate both the bandgap and band edge positions. Herein, we theoretically and experimentally demonstrate that oxygen vacancies occupied by boron-stabilized hydrogen pairs (OV_BH) serve as an integrative band modifier. Compared to hydrogen-occupied oxygen vacancies (OV_H), which require the aggregation of nanosized anatase TiO₂ particles, oxygen vacancies coupled with boron (OV_BH) can be easily introduced into large and highly crystalline TiO₂ particles, as shown by density functional theory (DFT) calculations. The coupling with interstitial boron facilitates the introduction of paired hydrogen atoms. The red-colored {001} faceted anatase TiO₂ microspheres with OV_BH benefit from the narrowed bandgap of 1.84 eV and the down-shifted band position. These microspheres not only absorb long-wavelength visible light up to 674 nm but also enhance visible-light-driven photocatalytic oxygen evolution.