Rationally controlled synthesis of transition metal oxide materials for structure-related applications in diverse areas at room temperature and ambient atmosphere remains a challenge. In this article, we propose a facile one-step calcination-free approach for the rational and green synthesis of 3D hierarchical polyhedron-shaped superstructures of manganese dioxide (MnO2) through the simultaneous ion exchange and oxidation of a preformed Mn-based M2(dobdc) (dobdc = 2,5-dihydroxy-1,4-benzenedicarboxylate) MOF (CPO-27-Mn) template with an adequate open aqueous alkaline solution of a moderate concentration at room temperature, as well as their application in rechargeable lithium cells. Concretely, we proposed that during the solution-phase process, upon exchange of the anionic dobdc4− ligand with OH−, the resultant intermediate manganese hydroxide reacts with dissolved O2 in solution to form MnO2. Electrochemical evaluation showed that the as-synthesized hierarchical MnO2 superstructures exhibited excellent electrochemical performance, including high reversible specific reversibility (866.4 mA h g−1), superior rate capability and long-term cycling stability (797.9 mA h g−1 after 300 cycles at 1000 mA g−1) when serving as anodes. This unique novel MOF-derived protocol provides an alternative perspective on the designed fabrication of advanced transition metal oxide functional nanomaterials.
