Eliminating Concentration Polarization with Cationic Covalent Organic Polymer to Promote Effective Overpotential of Nitrogen Fixation

Electrocatalytic nitrogen reduction reaction offers a sustainable alternative to the conventional Haber‐Bosch process. However, it is currently restricted by low effective overpotential due to the concentration polarization, which arises from accumulated products, ammonium, at the reaction interface. Here, a novel covalent organic polymer with ordered periodic cationic sites is proposed to tackle this challenge. The whole network exhibits strong positive charge and effectively repels the positively charged ammonium, enabling an ultra‐low interfacial product concentration, and successfully driving the reaction equilibrium to the forward direction. With the given potential unchanged, the suppressed overpotential can be much liberated, ultimately leading to a continuous high‐level reaction rate. As expected, when this tailored microenvironment is coupled with a transition metal‐based catalyst, a 24‐fold improvement is generated in the Faradaic efficiency (73.74 %) as compared with the bare one. The proposed strategy underscores the importance of optimizing dynamic processes as a means of improving overall performance in electrochemical syntheses. A novel covalent organic polymer with ordered periodic cationic sites is proposed to tackle the concentration polarization and drive the equilibrium of the nitrogen reduction reaction in the forward direction. With the given potential unchanged, the suppressed overpotential can be much liberated, ultimately leading to a 24‐fold improvement generated in the Faradaic efficiency (73.74 %).