This study reports a novel model system that breaks the constraints of Le Chatelier's principle in O₂ electroreduction in mixed dioxygen environments. By creating single-zinc vacancies in a crystal structure, the catalyst exhibits enzyme-like binding with enhanced selectivity to O₂, shifting the reaction pathway from the Langmuir-Hinshelwood to an upgraded triple-phase Eley-Rideal mechanism. This results in minimal activity alteration of H₂O₂ yields and Faradaic efficiencies across a wide range of O₂ levels (100%-21%) at current densities of 50-300 mA cm⁻², which contradicts the classical Le Chatelier's reaction kinetics. A standalone prototype device was built for high-rate H₂O₂ production from atmospheric air, achieving the highest Faradaic efficiencies of 87.8% at 320 mA cm⁻², surpassing state-of-the-art catalysts and approaching the theoretical limit for direct air electrolysis. Techno-economic analyses show that using atmospheric air feedstock offers 21.7% better economics compared to high-purity O₂, with the lowest H₂O₂ capital cost of 0.3 $ Kg⁻¹. This work highlights the potential for leveraging systems beyond the classical Le Chatelier principle in chemical and catalytic systems.This study reports a novel model system that breaks the constraints of Le Chatelier's principle in O₂ electroreduction in mixed dioxygen environments. By creating single-zinc vacancies in a crystal structure, the catalyst exhibits enzyme-like binding with enhanced selectivity to O₂, shifting the reaction pathway from the Langmuir-Hinshelwood to an upgraded triple-phase Eley-Rideal mechanism. This results in minimal activity alteration of H₂O₂ yields and Faradaic efficiencies across a wide range of O₂ levels (100%-21%) at current densities of 50-300 mA cm⁻², which contradicts the classical Le Chatelier's reaction kinetics. A standalone prototype device was built for high-rate H₂O₂ production from atmospheric air, achieving the highest Faradaic efficiencies of 87.8% at 320 mA cm⁻², surpassing state-of-the-art catalysts and approaching the theoretical limit for direct air electrolysis. Techno-economic analyses show that using atmospheric air feedstock offers 21.7% better economics compared to high-purity O₂, with the lowest H₂O₂ capital cost of 0.3 $ Kg⁻¹. This work highlights the potential for leveraging systems beyond the classical Le Chatelier principle in chemical and catalytic systems.