1e:T51b,Second-generation TiO(2)-(x)D(x) photocatalysts doped with either anions (N, C, and S mostly) or cations have recently been shown to have their absorption edge red-shifted to lower energies (longer wavelengths), thus enhancing photonic efficiencies of photoassisted surface redox reactions. Some of the studies have proposed that this red-shift is caused by a narrowing of the band gap of pristine TiO(2) (e.g., anatase, E(bg) = 3.2 eV; absorption edge ca. 387 nm), while others have suggested the appearance of intragap localized states of the dopants. By contrast, a recent study by Kuznetsov and Serpone (J. Phys. Chem. B, in press) has proposed that the commonality in all these doped titanias rests with formation of oxygen vacancies and the advent of color centers (e.g., F, F(+), F(++), and Ti(3+)) that absorb the visible light radiation. This article reexamines the various claims and argues that the red-shift of the absorption edge is in fact due to formation of the color centers, and that while band gap narrowing is not an unknown occurrence in semiconductor physics it does necessitate heavy doping of the metal oxide semiconductor, thereby producing materials that may have completely different chemical compositions from that of TiO(2) with totally different band gap electronic structures.1f:T4ad,Dinitrogen reduction to ammonia using transition metal catalysts is central to both the chemical industry and the Earth's nitrogen cycle. In the Haber-Bosch process, a metallic iron catalyst and high temperatures (400 °C) and pressures (200 atm) are necessary to activate and cleave NN bonds, motivating the search for alternative catalysts that can transform N₂ to NH₃ under far milder reaction conditions. Here, the successful hydrothermal synthesis of ultrathin TiO₂ nanosheets with an abundance of oxygen vacancies and intrinsic compressive strain, achieved through a facile copper-doping strategy, is reported. These defect-rich ultrathin anatase nanosheets exhibit remarkable and stable performance for photocatalytic reduction of N₂ to NH₃ in water, exhibiting photoactivity up to 700 nm. The oxygen vacancies and strain effect allow strong chemisorption and activation of molecular N₂ and water, resulting in unusually high rates of NH₃ evolution under visible-light irradiation. Therefore, this study offers a promising and sustainable route for the fixation of atmospheric N₂ using solar energy.

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