In situ fabrication of Mn3O4 decorated graphene oxide as a synergistic catalyst for degradation of methylene blue

• GO/Mn3O4 composites are successfully synthesized via a simple and green approach.
• The method avoids fussy procedure for the separation process.
• The atom-economic reaction produces only K2SO4 crystal as the by-product.
• GO/Mn3O4 composite exhibits a high efficiency in catalytic oxidation of MB at room temperature.
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• OH specie has a positive relation with the catalytic activity for degradation of MB.

Herein we report a one-step approach to the highly efficient synthesis of graphene oxide/Mn3O4 (GO/Mn3O4) hybrids with superior catalytic activities for decomposition of methylene blue (MB) in water. This method exploits the pristine graphene oxide/manganese sulfate (GO/MnSO4) suspension produced by the modified Hummers method as the raw materials, in which GO/MnSO4 has been in situ converted into GO/Mn3O4 hybrid in combination with KOH and air. This atom-economic reaction produces only K2SO4 crystal as the by-product which meets the standard of green chemistry. For catalystic degradation of MB dye at room temperature, the as-prepared GO/Mn3O4 catalysts result in a significant enhancement in the reaction rate compared to that of the bare Mn3O4 particles with the assistance of H2O2. Typically, 50 mL of MB (50 mg L−1) can be 100% decolorized and 77% mineralized with 10 mg of the GO/Mn3O4 hybrid. Such excellent catalytic performance of the GO/Mn3O4 hybrid is mainly attributed to the synergistic effects of GO, Mn3O4, H2O2 and MB molecules. Based on the hydroxyl radical experiments, the catalytic activity of GO/Mn3O4 hybrids for degradation of MB is closely related with the amount of the reactive
• OH species generated from H2O2.

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