Abstract The rational design of nonprecious bifunctional electrocatalysts for oxygen evolution/reduction reactions (OER/ORR) is critical yet challenging for sustainable energy systems. While long‐range synergistic (LRS) effects, governed by spatial arrangements and electronic coupling of active sites, critically influence metal coordination environments and orbital overlap for optimized intermediate adsorption, their fundamental mechanisms remain elusive. Herein, Co‐Cu dual‐atom sites within CeO 2 hollow spheres (CoCu@CeO 2 ) via an effective electrostatic adsorption strategy are anchored. The catalyst demonstrates low OER overpotential (235 mV @10 mA cm −2 ) and superior ORR activity (0.878 V vs RHE for half‐wave potential), surpassing most reported bifunctional systems. Mechanistic investigations reveal distinct reaction pathways: the OER predominantly occurs at Co sites, while Cu sites preferentially facilitate the ORR. Crucially, density functional theory calculations further demonstrate that LRS induces interfacial electron redistribution and modulates d ‐band centers, thereby optimizing the binding energies of key intermediates. This work proposes a novel mechanism for engineering dual‐atom architectures through long‐range electronic interactions, providing valuable insights into the advancement of advanced electrocatalysts for sustainable energy conversion systems.
Zhang et al. (2025) studied this question.