Electron Synergism in Boron Interstitial Doping Ordered Pt ₃ Co Nanoparticles Enhances the Protonation Process: Application to Efficient Oxygen Reduction in Zinc‐Air Batteries

Abstract Ordered intermetallic Pt ₃ Co compounds are highly promising alloy materials for oxygen electrocatalysis, while the sluggish kinetics and high cost of Pt still hinder their wide use in practical applications. In this work, boron atom gap‐doped Pt ₃ Co nanoparticles loaded on carbon nanobowls (B‐Pt ₃ Co/CNBs) are obtained to enhance the oxygen reduction reaction (ORR) performance. The introduction of B atoms is responsible for the negative shift of the d‐band center compared to Pt ₃ Co, and the subsequent reduction process leads to the uniform loading of B‐Pt ₃ Co nanoparticles on hollow carbon nanobowls. It is demonstrated that B‐Pt ₃ Co/CNBs exhibit the best electrocatalytic performance for ORR with an onset potential of 1.095 V versus RHE and a half‐wave potential of 0.985 versus RHE, as well as robust electrocatalytic stability with negligible activity decay even after 50 000 cycles. Experimental and theoretical calculations show that the introduction of the highly electronegative metalloid B leads the Pt atoms to lose electrons, which changes the electronic structure of Pt ₃ Co that can weaken the bonding strength of Pt‐O and accelerate the protonation and desorption of O* on the surface of the B‐Pt ₃ Co/ CNB, reducing the energy barrier of the rate‐determining step during the ORR process.