True Photoreactivity Origin of Ti³⁺-Doped Anatase TiO₂ Crystals with Respectively Dominated Exposed {001}, {101}, and {100} Facets

Abstract

Combining the advantages of reactive crystal facets and engineering defects is an encouraging way to address the inherent disadvantages of titanium dioxide (TiO₂) nanocrystals. However, revealing the true photoreactivity origin for defective TiO₂ with coexposed or predominant exposed anisotropic facets is still highly challenging. Here, the photoreactivity of TiO₂ nanocrystals with respectively predominant exposed {001}, {101}, and {100} facets before and after Ti³⁺ doping under both ultraviolet and visible light was compared systematically. In detail, the photocatalytic H₂ production for R-TiO₂-001, R-TiO₂-101, and R-TiO₂-100 increased by a factor of 1.34, 2.65, and 3.39 under UV light and a factor of 8.90, 13.47, and 8.72 under visible light. By contrast, the photocatalytic degradation of methyl orange for R-TiO₂-001, R-TiO₂-101, and R-TiO₂-100 increased by a factor of 3.18, 1.42, and 2.17 under UV light and a factor of 4.03, 2.85, and 1.58 under visible light, respectively. The true photocatalytic activity origin for the obtained photoreduction and photo-oxidation ability is attributed to the exposure of more active sites (under-coordinated 5-fold Ti atoms), the facilitated charge transfer among {001}, {101}, and {100} facets, and the Ti³⁺ energy state with variable doping levels to extend the visible light response. This work hopefully provides significant insights into the photoreactivity origin of defective TiO₂ nanocrystals with anisotropic exposed facets.