Circumventing Scaling Relations via Gradient Orbital Coupling Promotes Ammonia Electrosynthesis on Cobalt Catalyst

Abstract Highly efficient electrocatalytic nitrate reduction to ammonia (NH 3 ) relies on the balanced activation of various substrates including nitrate and water, but is currently hindered by the inherent scaling relations governing the adsorption of key reaction intermediates, such as *NO and *H. Herein, we develop a strategy to circumvent these limitations by introducing f–d–p gradient orbital coupling in cobalt oxide (Co 3 O 4 ) through Ce doping. Density functional theory calculations indicate that the lattice strain triggered by the dopant redistributes electron density at the Co and O sites, thereby modulating the adsorption strengths of *NO and *H, which favors the production of NH 3 while suppressing hydrogen evolution reaction. It exhibits a faradaic efficiency of 97.8% and a high yield rate of 3423.0 µg h −1 cm −2 under alkaline conditions. Furthermore, Ce/Co 3 O 4 catalyst shows robust performance over a wide range of nitrate concentrations (from 5 to 200 mM) and excellent cycling stability. Our findings also suggest that the gradient orbital coupling approach can be extended to other lanthanide dopants (e.g., Pr and Nd), offering a broadly applicable platform to break scaling relations and improve NO 3 − ‐to‐NH 3 activity on cobalt catalysts.