A DFT Investigation of B‐Doped C3N as Single Atom Electrocatalysts for N2‐to‐NH3 Conversion

Abstract The NH 3 synthesis from N 2 plays an important role in the ecological cycle and industrial production. Different from industrial NH 3 synthesis with high pollution and energy consumption, electrocatalytic NH 3 synthesis is favored because of its environmental protection, energy saving, ambient reaction conditions and other characteristics. However, due to the low efficiency and poor reaction selectivity of the existing electrocatalysts, which can not be used actually, the development of new electrocatalysts for nitrogen reduction reaction (NRR) is particularly urgent. Herein, we designed a series of transition metal atoms anchored B‐doped defective C 3 N surface (TM@B 2 C 3 N) as single‐atom catalysts. Through the screening process of N 2 adsorption activation, N 2 H formation and NH 3 desorption, finally the excellent electrocatalysts with strong stability and high activity (Cr@B 2 C 3 N and Mn@B 2 C 3 N) were obtained. After simulating the entire pathway, it was found that the NRR process on Cr@B 2 C 3 N and Mn@B 2 C 3 N via consecutive and distal pathways with the lowest limiting potential of −0.42 and −0.52 V, which have the good ability to inhibit hydrogen evolution reaction. Finally, the electronic properties were analyzed, and the reason for their high catalytic activity was summarized. This work provides a new idea for the rational design of NRR electrocatalysts and promotes the practical application of electrocatalysts.