Dinesh Shetty

The electrocatalytic nitrogen reduction reaction (NRR) driven by renewable electricity provides a green synthesis route for ammonia (NH 3 ) production under ambient conditions but suffers from a low conversion yield and poor Faradaic efficiency (F.E.) because of strong competition from hydrogen evolution reaction (HER) and the poor solubility of N 2 in aqueous systems. Herein, an in situ proton filter covalent organic framework catalyst ( Ru‐Tta‐Dfp ) is reported with inherent Ruthenium (Ru) sites where the framework controls reactant diffusion by suppressing proton supply and enhancing N 2 flux, causing highly selective and efficient catalysis. The smart catalyst design results in a remarkable ammonia production yield rate of 2.03 mg h −1 mg cat −1 with an excellent F.E. of ≈52.9%. The findings are further endorsed with the help of molecular dynamics simulations and control COF systems without in situ proton filter feasibility. The results point to a paradigm shift in engineering high‐performance NRR electrocatalysts for more feasible green NH 3 production.