Foamer-Derived Bulk Nitrogen Defects and Oxygen-Doped Porous Carbon Nitride with Greatly Extended Visible-Light Response and Efficient Photocatalytic Activity.

Constructing bulk defects and doping are feasible ways to essentially narrow the band gap and improve the light absorption of photocatalysts. Herein, inspired by bread foaming, the foaming agent azoformamide or azodicarbonamide (AC) was introduced during the thermal polymerization of urea. In the polymerization process, a large number of bubbles produced by AC decomposition seriously interfered with the polymerization of urea, resulting in the breaking of the hydrogen bonds and van der Waals interaction in carbon nitride, distortion of its structure, and partial oxidation, thus forming a series of porous carbon nitrides U/ACx (x is the ratio of AC to urea; where x = 0.25, 0.5, and 1) with bulk N defects and O doping. Its band gap was reduced to 1.91 eV and the absorption band edge was greatly extended to 650 nm. The optimal U/AC0.5 exhibits the highest visible light photocatalytic hydrogen production rate of about 44.7 μmol·h-1 (10 mg catalysts) and shows superior photocatalytic performance for the oxidation of diphenylhydrazine to azobenzene, with conversion and selectivity of almost 100%, and is one of the most active defective carbon nitrides, especially under long-wavelength (λ ≥ 550 nm) light irradiation. It paves the way for the design of highly efficient and wide-spectral-response photocatalysts.