Integrated MnO2 nanosheet ultrafiltration ceramic membrane with micro-nano bubbles for catalytic treatment of dye wastewater

Membrane filtration integrated with micro-nano bubbles (MNBs) is an attractive technology for treating dye wastewater given its efficiency and environmental compatibility. However, the amount of ·OH generated during the disintegration of MNBs is insufficient in practical applications. This work presents the characterisation of a modified Al2O3 ceramic membrane (CM) with the MnO2 nanosheet (MnO2/Al2O3 CM), which provides dual functions of membrane filtration and MNB catalysis. Here, a novel MNB catalytic membrane reactor (MNB-CMR) was constructed by applying the modified MnO2/Al2O3 CM for treating the simulated dye wastewater, i.e., methylene blue (MB). The MB degradation showed that the MNB-CMR improved 17% decolorization rate and 20% total organic carbon removal rate compared to the integrated MNB process with the non-modified CM. The MNB-CMR exhibited excellent catalytic performance and fouling resistance. Besides, the effects of MNB-CMR operational parameters such as the initial methylene blue (MB) concentration, reaction temperature, solution flux, and solution pH on the MB degradation performance were investigated. Based on the scavenging experiments of reactive oxygen species (ROS), the reaction of singlet oxygen (1O2) or hydroxyl radicals (·OH) was elucidated as the primary ROS responsible for the oxidation of MB in the MNB-CMR. In addition, the XPS results showed that the redox couple of Mn(IV)/Mn(III) on the surface of the MnO2/Al2O3 CM was responsible for MNB catalysis. Finally, we proposed a possible degradation pathway of MB. This work shows an attractive alternative wastewater treatment process to relieve membrane fouling and enhance MNB catalysis concurrently.