Skin B/N-doped anatase TiO₂ {001} nanoflakes for visible-light photocatalytic water oxidation

The limited visible-light-responsive photoactivities of most doped wide-bandgap photocatalysts with widened absorption range have long been the obstacles for the efficient conversion of solar energy to chemical energy by photocatalysis. The weak transport ability of visible-light-induced low-energy charge carriers, and numerous recombination centers arising from the energy-band modifiers along the transport path are two major factors responsible for such a mismatch. A potential solution is to shorten the transport path of photo-induced charges in well-modulated light absorbers with low-dimensional structure and the spatially concentrated dopants underneath their surfaces. As a proof of concept, skin B/N-doped red anatase TiO₂ {001} nanoflakes with the absorption edge up to 675 nm were synthesized in this study. Experimental results revealed that boron dopants in the TiO₂ nanoflakes from the hydrolysis of nanosized TiB₂ played a crucial role in controlling nitrogen doping in the surface layer of the nanoflakes. As visible light excitation occurs at the surface layer, the photons can be sufficiently absorbed by the formed energy levels at the surface layers, and the photogenerated charge carriers can effectively migrate to the surface, thus leading to efficient visible-light-responsive photocatalytic oxygen evolution activity from water oxidation.