Molecular Imprinting Technology Enables Proactive Capture of Nitrogen for Boosted Ammonia Synthesis under Ambient Conditions

Electrochemical nitrogen reduction reaction (NRR) is a burgeoning field for green and sustainable ammonia production, in which numerous potential catalysts emerge endlessly. However, satisfactory performances are still not realized under practical applications due to the limited solubility and sluggish diffusion of nitrogen at the interface. Herein, molecular imprinting technology is adopted to construct an adlayer with abundant nitrogen imprints on the electrocatalyst, which is capable of selectively recognizing and proactively aggregating high‐concentrated nitrogen at the interface while hindering the access of overwhelming water simultaneously. With this favorable microenvironment, nitrogen can preferentially occupy the active surface, and the NRR equilibrium can be positively shifted to facilitate the reaction kinetics. Approximately threefold improvements in both ammonia production rate (185.7 µg h−1 mg−1) and Faradaic efficiency (72.9%) are achieved by a metal‐free catalyst compared with the bare one. It is believed that the molecular imprinting strategy should be a general method to find further applicability in numerous catalysts or even other reactions facing similar challenges. Molecular imprinting technology is adopted to construct an adlayer with abundant nitrogen imprints on the electrocatalyst to selectively recognize and proactively aggregate high‐concentrated nitrogen at the interface while hindering access to overwhelming water simultaneously. Threefold improvements in both ammonia production rate and Faradaic efficiency are achieved by a metal‐free catalyst compared with the bare one.