Fe-species-loaded mesoporous MnO2 superstructural requirements for enhanced catalysis.

In this work, a novel catalyst, Fe-species-loaded mesoporous manganese dioxide (Fe/M-MnO2) urchinlike superstructures, has been fabricated successfully in a two-step technique. First, mesoporous manganese dioxide (M-MnO2) urchinlike superstructures have been synthesized by a facile method on a soft interface between CH2Cl2 and H2O without templates. Then the M-MnO2-immobilized iron oxide catalyst was obtained through wetness impregnation and calcination. Microstructural analysis indicated that the M-MnO2 was composed of urchinlike hollow submicrospheres assembled by nanorod building blocks with rich mesoporosity. The Fe/M-MnO2 retained the hollow submicrospheres, which were covered by hybridized composites with broken and shortened MnO2 nanorods. Energy-dispersive X-ray microanalysis was used to determine the availability of Fe loading processes and the homogeneity of Fe in Fe/M-MnO2. Catalytic performances of the M-MnO2 and Fe/M-MnO2 were evaluated in catalytic wet hydrogen peroxide oxidation of methylene blue (MB), a typical organic pollutant in dyeing wastewater. The catalytic degradation displayed highly efficient discoloration of MB when using the Fe/M-MnO2 catalyst, e.g., ca. 94.8% of MB was decomposed when the reaction was conducted for 120 min. The remarkable stability of this Fe/M-MnO2 catalyst in the reaction medium was confirmed by an iron leaching test and reuse experiments. Mechanism analysis revealed that the hydroxyl free radical was responsible for the removal of MB and catalyzed by M-MnO2 and Fe/M-MnO2. MB was transformed into small organic compounds and then further degraded into CO2 and H2O. The new insights obtained in this study will be beneficial for the practical applications of heterogeneous catalysts in wastewater treatments.