Transition metal ions-modified birnessite toward highly efficiency photocatalytic formaldehyde oxidation under visible light irradiation.

Accelerating the interfacial charge transfer process (ICTS) of the catalysts can immensely improve the photocatalytic efficiency. Doping transition metal ions not only promote the ICTS, but also boost multielectron reduction reactions of oxygen. Herein, birnessite-type MnO2 have been modified by different transition metal ions (TM = Zn2+, Cu2+, and Fe3+) in this work. Post-doping, Fe-Birnessite was featured by the highest photocatalytic HCHO oxidation activity with 80 ppm of HCHO which presented complete removal of HCHO for 80 min, while K-, Cu-, and Zn-Birnessite took 105, 135, and 170 min, respectively. In detail, the photoexcited electrons were caught by Fe (III) and then generated Fe (II),which could continue to capture photoexcited electrons to produce Fe (I) under visible light; on the other hand, the Fe (I) could be oxidized by O2 to obtain Fe (II) and then recover to Fe (III). This process tremendously improved the ICTS.