Synthesis and photocatalytic activity of perovskite niobium oxynitrides with wide visible-light absorption bands.

Photocatalytic activities of perovskite-type niobium oxynitrides (CaNbO₂N, SrNbO₂N, BaNbO₂N, and LaNbON₂) were examined for hydrogen and oxygen evolution from water under visible-light irradiation. These niobium oxynitrides were prepared by heating the corresponding oxide precursors, which were synthesized using the polymerized complex method, for 15 h under a flow of ammonia. They possess visible-light absorption bands between 600-750 nm, depending on the A-site cations in the structures. The oxynitride CaNbO₂N, was found to be active for hydrogen and oxygen evolution from methanol and aqueous AgNO₃, respectively, even under irradiation by light at long wavelengths (λ<560 nm). The nitridation temperature dependence of CaNbO₂N was investigated and 1023 K was found to be the optimal temperature. At lower temperatures, the oxynitride phase is not adequately produced, whereas higher temperatures produce more reduced niobium species (e. g., Nb³(+) and Nb⁴(+)), which can act as electron-hole recombination centers, resulting in a decrease in activity.