Controllable Exfoliation of MOF‐Derived Van Der Waals Superstructure into Ultrathin 2D B/N Co‐Doped Porous Carbon Nanosheets: A Superior Catalyst for Ambient Ammonia Electrosynthesis

Abstract The electrocatalytic nitrogen reduction reaction (NRR) to synthesize NH 3 under ambient conditions is a promising alternative route to the conventional Haber–Bosch process, but it is still a great challenge to develop electrocatalysts’ high Faraday efficiency and ammonia yield. Herein, a facile and efficient exfoliation strategy to synthesize ultrathin 2D boron and nitrogen co‐doped porous carbon nanosheets (B/NC NS) via a metal–organic framework (MOF)‐derived van der Waals superstructure, is reported. The results of experiments and theoretical calculations show that the doping of boron and nitrogen can modulate the electronic structure of the adjacent carbon atoms; which thus, promotes the competitive adsorption of nitrogen and reduces the energy required for ammonia synthesis. The B/NC NS exhibits excellent catalytic performance and stability in electrocatalytic NRR, with a yield rate of 153.4 µg·h −1 ·mg −1 cat and a Faraday efficiency of 33.1%, which is better than most of the reported NRR electrocatalysts. The ammonia yield of B/NC NS can maintain 92.7% of the initial NRR activity after 48 h stability test. The authors’ controllable exfoliation strategy using MOF‐derived van der Waals superstructure can provide a new insight for the synthesis of other 2D materials.