Decoupling Adsorption of Key Intermediates Enabled by Asymmetric 3d‐5d‐Orbital Hybridization: Durable High‐Performance AEM Water Electrolysis and Zn–Air Batteries

Abstract Decoupling key intermediates’ adsorption via asymmetric 3d‐5d‐orbital hybridization overcomes the intrinsic scaling relation bottleneck, enabling rational design of high‐performance, durable multifunctional electrocatalysts for anion exchange membrane water electrolyzers (AEMWEs) and Zn–air batteries (ZABs). Here, we reveal that asymmetric 3d‐5d‐orbital hybridization, engineered through the synergy of lattice strain and defect structures in a nitrogen‐doped carbon‐supported PtCo alloy (PtCo@NPC), effectively decouples these adsorption energies of key intermediates. PtCo@NPC demonstrates exceptional multifunctional electrocatalytic performance for the hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction in alkaline media. Density functional theory calculations suggest that electronic structure modulation tunes the adsorption characteristics of intermediates, while X‐ray absorption fine structure spectroscopy confirms the corresponding changes in the electronic states of surface Pt and Co atoms. When deployed in devices, PtCo@NPC enables AEMWEs to operate stably for 522 h at 1000 mA cm −2 with a voltage decay rate of only 0.103 mV h −1 and empowers ZABs to achieve a long cycle life of over 2520 cycles at 5.0 mA cm −2 . This study highlights electronic‐structure modulation as a powerful strategy for advanced energy technologies.