The exploration of a non-precious metal bifunctional electrocatalyst with novel structures for the efficient oxygen reduction reaction (ORR) and oxygen evolution reactions (OER) remains a great challenge. Multidimensional assembled nanostructures with nitrogen-doped carbon matrix inlaid with transition-metal (M-N-C) can be used as efficient electrocatalysts due to its large surface area and highly revealed active sites. Herein, we report an anion-mediated self-template one-step in situ transformation into multidimensional hierarchical nano-assembled M-N-C catalysts, which is assembled from 0D cobalt nanoparticles terminally inlaid in 1D carbon nanotubes growing on a honeycomb-like ultrathin 3D carbon network (denoted as Co@N-CNTs/CS). By further synthetic process characterization, the nitrate-mediated structural evolution during rising thermal stages is disclosed. Thanks to the fully exposed surfaces and highly accessible active sites in the unique multidimensional structure, our developed catalyst exhibits a large surface area and enhanced performance in bifunctional oxygen redox in alkaline media, which further endows potentials in rechargeable Zn-air batteries, surpassing the typical benchmark catalysts Pt/C + Ir/C. Our study affords a fresh path to facile fabrication of M-N-C electrocatalysts.
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