Abstract
Titanium dioxide (TiO2) is widely recognized as one of the most promising
photocatalysts for solar energy utilization and environmental cleanup, but because of its wide bandgap, pure TiO2 can only absorbs ultraviolet light, which represents 4% of the solar spectrum1-6. Here we establish a conceptually novel approach, termed non-compensated n-p codoping, to narrow the bandgap of TiO2 and shift the optical response into the visible spectral range where a much larger fraction of the solar spectrum can be captured. The concept embodies two key ingredients: The electrostatic attraction within the n-p dopant pair enhances the thermodynamic and kinetic solubility in substitutional doping, and the non-compensated nature ensures the creation of broadened intermediate electronic states that effectively narrow the bandgap. The concept is demonstrated quantitatively within first-principles density functional theory. The experimental evidence for bandgap narrowing is obtained in the forms of direct measurements of the density of states by scanning tunneling spectroscopy, dramatically redshifted and increased optical absorbance, and enhanced photoactivity manifested by efficient hole-electron separation in the visible spectral region. These findings represent the first crucial steps toward development of a new class of titania-based photocatalysts with greatly enhanced efficiency of solar energy conversion facilitating environmentally friendly applications ofrenewable energy.
