Hydrophobic Microenvironment Modulation of Ru Nanoparticles in Metal–Organic Frameworks for Enhanced Electrocatalytic N₂ Reduction

Abstract The modulation of the chemical microenvironment surrounding metal nanoparticles (NPs) is an effective means to enhance the selectivity and activity of catalytic reactions. Herein, a post‐synthetic modification strategy is developed to modulate the hydrophobic microenvironment of Ru nanoparticles encapsulated in a metal–organic framework (MOF), MIP‐206, namely Ru@MIP‐F_x (where x represents perfluoroalkyl chain lengths of 3, 5, 7, 11, and 15), in order to systematically explore the effect of the hydrophobic microenvironment on the electrocatalytic activity. The increase of perfluoroalkyl chain length can gradually enhance the hydrophobicity of the catalyst, which effectively suppresses the competitive hydrogen evolution reaction (HER). Moreover, the electrocatalytic production rate of ammonia and the corresponding Faraday efficiency display a volcano‐like pattern with increasing hydrophobicity, with Ru@MIP‐F₇ showing the highest activity. Theoretical calculations and experiments jointly show that modification of perfluoroalkyl chains of different lengths on MIP‐206 modulates the electronic state of Ru nanoparticles and reduces the rate‐determining step for the formation of the key intermediate of N₂H₂^*, leading to superior electrocatalytic performance.