Red anatase TiO2 microspheres with exposed major {001} facets and boron-stabilized hydrogen-occupied oxygen vacancies for visible-light- responsive water oxidation

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 simultane-ously modulate both the bandgap and band edge positions. Herein, we theoretically and experimentally demonstrate that oxygen vacancies occupied by boron-stabilized hydrogen pairs (OVBH) serve as an inte-grative band modifier. Compared to hydrogen-occupied oxygen vacancies (OVH), which require the aggregation of nanosized anatase TiO2 particles, oxygen vacancies coupled with boron (OVBH) 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 OVBH 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.(c) 2023 Elsevier Inc. All rights reserved.