A bonded phosphorus source strategy for Co-Co2P heterojunction catalysts via In Situ phase reconstruction toward long-life zinc-air batteries

Heterostructured composites have emerged as pivotal platforms for multifunctional electrocatalysis, where in-situ synthesis strategies prove critical in constructing atomically precise interfaces. However, precisely engineering such interfaces with favorable electronic structures and optimized adsorption energetics remains a significant challenge. To address this, we report a dynamic phase-reconstruction strategy by a bonded phosphorus source strategy enabling the spontaneous formation of Co-Co 2 P heterointerfaces within a three-dimensional N, P-codoped carbon architecture (Co-Co 2 P@HNPC), engineered through molecular self-assembly of histidine-phytic acid supramolecular complexes with cobalt ions. The metallic Co-Co bonds and Co-P coordination reveals charge redistribution at heterointerfaces through strengthened Co-N-C bonding networks. DFT result demonstrates that the reconfigured heterointerface synergistically optimizes d -band center positioning via p - d orbital hybridization, concurrently lowering the Gibbs free energy barriers for both ORR and OER. The optimized catalyst achieves low overpotentials (η OER = 1.63 V @10 mA cm −2 ; E 1/2 = 0.83 V) and exceptional rechargeable Zn-air battery performance, with a lifespan exceeding 1200 h and a peak power density of 201 mW cm −2 . This study introduces a dynamic phosphidation engineering strategy, utilizing chemical anchoring of P-precursors, providing new insights for designing effective heterointerface electrocatalysts. A bonded phosphorus source strategy and in-situ phase reconstruction were developed to fabricate Co-Co 2 P@HNPC bifunctional electrocatalysts. Co-Co2P@HNPC shows excellent ORR/OER activity (ηOER=1.63 V @10 mA cm- 2 , E1/2=0.83 V). The assembled Zn-air battery delivers 201 mW cm- 2 peak power density and >1200 h durability. p-d orbital hybridization at Co-Co 2 P heterointerfaces optimizes oxygen intermediate adsorption.