The study reports an efficient Zr-NiO catalyst for the electrochemical reduction of nitrite (NO₂⁻) to ammonia (NH₃), offering a green route to NH₃ synthesis. The catalyst, with atomically dispersed Zr-dopants in the NiO lattice, demonstrates exceptional performance at industrial-level current densities (>0.2 A cm⁻²). In situ spectroscopic measurements and theoretical simulations reveal the formation of Zr-Ni frustrated Lewis acid-base pairs (FLPs) on Zr-NiO, which enhance the absorption of NO₂⁻, promote its activation and protonation, and reduce hydrogen coverage, thereby improving activity and selectivity. Notably, Zr-NiO achieves a high Faradaic efficiency for NH₃ of 94.0% and an NH₃ yield rate of 1,394.1 μmol h⁻¹ cm⁻² at a current density of 228.2 mA cm⁻², making it one of the best NO₂RR electrocatalysts for NH₃ production. The research highlights the potential of FLPs in enhancing the efficiency of NO₂RR processes.The study reports an efficient Zr-NiO catalyst for the electrochemical reduction of nitrite (NO₂⁻) to ammonia (NH₃), offering a green route to NH₃ synthesis. The catalyst, with atomically dispersed Zr-dopants in the NiO lattice, demonstrates exceptional performance at industrial-level current densities (>0.2 A cm⁻²). In situ spectroscopic measurements and theoretical simulations reveal the formation of Zr-Ni frustrated Lewis acid-base pairs (FLPs) on Zr-NiO, which enhance the absorption of NO₂⁻, promote its activation and protonation, and reduce hydrogen coverage, thereby improving activity and selectivity. Notably, Zr-NiO achieves a high Faradaic efficiency for NH₃ of 94.0% and an NH₃ yield rate of 1,394.1 μmol h⁻¹ cm⁻² at a current density of 228.2 mA cm⁻², making it one of the best NO₂RR electrocatalysts for NH₃ production. The research highlights the potential of FLPs in enhancing the efficiency of NO₂RR processes.