Transition-metal-based multifunctional catalysts have attracted increasing attention owing to high possibilities of substituting the expensive noble-metal-based catalysts in various scenarios. Multivariate metal-organic frameworks (MTV-MOFs) are ideal precursors to prepare multimetallic nanocomposites with high catalytic activity since the uniform distribution and precise regulation of mixed metal centers, as well as the consequent strong synergistic effect, could be readily achieved. Herein, a Mn/Co/Ni trimetallic catalyst (MnCoNi-C-D) with a hollow rhombic dodecahedron shape was synthesized via pyrolysis of the corresponding trimetallic-based MTV-MOF. The catalyst shows outstanding electrochemical activity toward the oxygen reduction reaction including a half-wave potential of 0.82 V and superior tolerance against methanol as well as high stability in an alkaline medium, and its oxygen evolution reaction activity also surpasses a RuO2 catalyst. Moreover, primary and rechargeable zinc-air batteries based on MnCoNi-C-D delivered preferable performances compared with commercial Pt/C-RuO2, including higher peak power density (116.4 mW cm-2), higher specific capacity (841.3 mAh g-1), higher open-circuit potential (OCV) (1.46 V), and better stability for more than 180 h. A comprehensive comparison was also conducted to prove the necessity of employing the MTV-MOF as the precursor and investigate the intrinsic superiority of the catalyst.
Keywords: Zn−air batteries; bifunctionality; metal−organic framework; multivariate; oxygen evolution reaction; oxygen reduction reaction; transition metal.