Synergistic space-electron regulation under interlayer confinement: Disrupting oxygen evolution/reduction reaction scaling relations via dual-pathway control.

Oxygen evolution and reduction reactions (OER/ORR) are fundamental to energy conversion technologies such as water electrolyzers and fuel cells. However, the intrinsic linear scaling relationship (LSR) between the intermediate adsorption energies limits catalytic activity. Overcoming this limitation could surpass the conventional activity-volcano relationship and unlock high-performance OER/ORR electrocatalysts. Herein, we propose a novel interlayer-confinement engineering strategy, utilizing spatially confined dual active sites in interlayer-confined dual single-atom-catalysts (iDSACs), to fundamentally break the intrinsic LSR by simultaneously manipulating reaction pathways and intermediate adsorption. Density functional theory (DFT) computations demonstrate that the synergistic space-electron effects enhance charge transfer, activate the O-O bond, and facilitate its dissociation. Further, tuning the confinement strength exerts opposing effects on various intermediates and catalysts. Consequently, this strategy effectively disrupts the LSR between *OOH and *OH adsorption, thereby improving OER and ORR activities. Additionally, an optimal interlayer distance of 7.0 Å is identified to balance dual-site synergy and steric effects, achieving low overpotentials (0.26 V for OER and 0.30 V for ORR on IrN4). This work establishes space-electron synergy as a generic platform to disrupt adsorption scaling laws, advancing efficient electrocatalyst design and providing fundamental insights into confined electrocatalysis.