Developing efficient and durable air cathodes is pivotal yet challenging for high-performance rechargeable zinc-air batteries (ZABs).‌ Herein, we present an innovative strategy that leverages oxidized graphdiyne (GDYO) as a multifunctional mediator to construct amorphous high-entropy sulfide-graphdiyne oxide composite (a-HESs-GDYO). The unique characteristics of GDYO, including its abundant oxygen-containing groups, electron-rich alkyne bonds, and triangular nanopores, exerts triple synergistic regulatory effects. This mechanism involves the coordinated dispersion of metal cations, electrostatic anchoring of metal nuclei, and confined growth within the pores, effectively addressing the common synthesis challenges of easy crystallization and elemental segregation encountered in amorphous high-entropy sulfides (a-HESs). Leveraging the GDYO-induced amorphous structure, the synergistic effect among multimetal components of high-entropy sulfides, as well as stable structural reconstruction and anti-agglomeration capability, a-HESs-GDYO delivers good dual-functional catalytic performance in zinc–air batteries. Specifically, the ‌a-HESs-GDYO catalyst exhibits enhanced electrocatalytic activity towards the oxygen reduction reaction (ORR)‌, showcasing a half-wave potential of 0.66 V (vs. RHE) and superior stability, representing an increase of 60 mV compared to crystalline HESs. When assembled as the air cathode of ZABs, the device demonstrates impressive performance, delivering a power density of ‌133 mW cm^-2‌, a specific capacity of ‌725 mAh g^-1‌, and long-term stability exceeding ‌1500 h‌ of operation. This study provides an effective and general synthetic strategy for high-performance amorphous high-entropy catalysts and establishes a robust paradigm for their application in next-generation energy storage devices.

Graphdiyne (GDY) is fascinating in the construction of efficient and stable catalysts, but their performance is still somewhat restricted due to GDY’s thicker layers, as well as hydrophobic and relatively chemically inert surfaces. Herein, via oxidation-exfoliation-reduction strategy, the self-supported electrode material of CoP nanosheets with ultrathin oxygen-containing GDY wrapping (CoP@RGDYO) for effective HER is constructed. The wrapping of ultrathin oxygen-containing GDY promotes charge transfer, improves the surface property, and enhances the acid and alkali resistance as well as the structural stability of the catalyst. As a result, CoP@RGDYO shows enhanced activity and stability in both acidic and alkaline media. Especially, it exhibits a low overpotential of 86 mV and exceptional stability under a 14000-cycle cyclic voltammetry scanning in alkaline media. This work provides new ideas for the design of GDY hybrid materials and the preparation of high-efficiency catalysts.