Phosphorus-induced 0D/1D intertwined N, P-codoped Fe-N-C hierarchical architectures for highly stable zinc-air batteries

A unique 3D hierarchical network consisting of 0D carbon dodecahedra and 1D carbon nanotubes is successfully constructed via in-situ growth. • Phosphorus doping serves as a versatile modulator to induce 1D morphology formation and optimize the electronic density of iron active centers. • The optimized N, P co-doped Fe-N-C catalyst exhibits an outstanding half-wave potential of 0.884 V in alkaline media. • The assembled zinc-air battery achieves a remarkable operational lifespan exceeding 1300 h with superior structural integrity. Developing highly efficient and durable non-precious metal electrocatalysts for oxygen reduction reaction (ORR) remains a critical challenge for the practical application of zinc-air batteries (ZABs). Herein, we successfully synthesized a robust N, P-codoped Fe-N-C catalyst featuring a unique 0D/1D intertwined architecture through a phosphorus-induced heteroatom-modulation strategy. By utilizing FePc-encapsulated ZIF-8 as a precursor, the in-situ growth of 1D carbon nanotubes from 0D carbon dodecahedrons was achieved, constructing a 3D hierarchical conductive network. Experimental and mechanistic analyses reveal that P-doping serves as the key morphology director. It not only induces the formation of structural-stable 1D nanotubes to enhance electron transfer but also modulates the electronic density of Fe centers to elevate electro-oxidation resistance. Consequently, the optimized catalyst exhibits a superior half-wave potential (E 1/2 ) of 0.884 V (vs. RHE) in alkaline media. Remarkably, the as-assembled ZAB achieves an exceptional stability of over 1300 h, demonstrating the superior structural integrity and durability of the 0D/1D network. This research offers a strategic design for engineering high-performance and stable Fe-N-C catalysts through synergistic 0D/1D architecture construction. Phosphorus-induced modulation facilitates the in-situ growth of 1D nanotubes from 0D dodecahedrons, constructing an integrated 0D/1D hierarchical Fe-N-C structure. This structural engineering optimizes the electronic environment of Fe sites for enhanced ORR kinetics (E 1/2  = 0.884 V) and endows practical zinc-air batteries with an outstanding stability exceeding 1300 h. Download: Download high-res image (283KB) Download: Download full-size image