Well‐Dispersed Entropy‐Driven Alloy Particles on Carbon Black From Stepwise Alloying Strategy and Their Bifunctional Electrocatalytic Performance for Zinc–Air Batteries

ABSTRACT The rational design of highly active and durable bifunctional electrocatalysts is essential for advancing next‐generation energy conversion and storage technologies. Herein, we report a stepwise alloying strategy for synthesizing ultrasmall, well‐dispersed entropy‐driven nanoparticles with a Pt‐centered structure incorporating Fe, Co, Ni, and Cu supported on cost‐effective carbon black (SA‐CB). Electrochemical studies demonstrate that SA‐CB exhibits outstanding bifunctional performance, with an onset potential of 1.01 V and a half‐wave potential of 0.84 V for the oxygen reduction reaction, together with a low oxygen evolution reaction overpotential of 0.36 V at 10 mA cm ⁻² . Importantly, when integrated into rechargeable zinc–air batteries (ZABs), SA‐CB delivers an open‐circuit voltage of 1.48 V, a peak power density of 114.6 mW cm ⁻² , and a specific capacity of 725.0 mAh g _Zn ⁻¹ , surpassing state‐of‐the‐art benchmarks. Density functional theory calculation provides a new mechanistic paradigm including multi‐metal‐induced d ‐band modulation and optimal d‐/p ‐band alignment, which uniquely enables balanced adsorption of electrocatalytic intermediates. These results establish stepwise alloying as an effective strategy for tailoring the structural and electronic properties of entropy‐driven nanoparticle catalysts and highlight their practical promise for high‐performance, sustainable ZABs.