Close inspection of the pre-edge in oxygen near-edge X-ray absorption fine structure spectra of single-step, gas-phase-synthesized titanium oxynitride photocatalysts with 20 nm particle size reveals an additional e g resonance in the valence band that went unnoticed in previous TiO 2 anion doping studies. The relative spectral weight of this Ti(3d)−O(2p) hybridized state with respect to and located between the readily established t 2g and e g resonances scales qualitatively with the photocatalytic decomposition power, suggesting that this extra resonance bears co-responsibility for the photocatalytic performance of titanium oxynitrides at visible light wavelengths.
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