Hydrophobic Nanoporous Silver with ZIF Encapsulation for Nitrogen Reduction Electrocatalysis

Electrochemical nitrogen reduction reaction (ENRR) offers a sustainable alternative to the environmentally hazardous Haber–Bosch process for producing ammonia. However, it suffers from an unsatisfactory performance due to its limited active sites and competitive hydrogen evolution reaction. Herein, we design a hydrophobic oleylamine-modified zeolitic imidazolate framework-coated nanoporous silver composite structure (NPS@O-ZIF). The composite achieves a high ammonia yield of (41.3 ± 0.9) μg·h(−1)·cm(−2) and great Faradaic efficiency of (31.7 ± 1.2)%, overcoming the performances of NPS@ZIF and traditional silver nanoparticles@O-ZIF. Our strategy affords more active sites and accessible channels for reactant species due to the porous structure of NPS cores and restrains the evolution of hydrogen by introducing the hydrophobic molecule coated on the ZIF surfaces. Hence, the design of the hydrophobic core–shell composite catalyst provides a valuably practical strategy for ENRR as well as other water-sensitive reactions.