▎ 摘　　要

In this work, graphene with SiC3 ligand is proposed as a high-performance nitrogen reduction reaction (NRR) electrocatalyst using density functional theory simulations. The Si atom holds a high positive charge which enable it to accommodate the lone pair electrons on N2, resulting in the capture of N2. More importantly, the electrocatalyst presents the minimum change of Gibbs free energy (0.19 eV) at the potential determining step (*N-N ->*N-NH) and the minimum overpotentials (0.03 V) among reported metal-free electrocatalysts. The introduction of SiC3 ligand does not impair the conductivity of graphene. Additionally, the electrocatalyst is stable at 298 K and solvation environment using the ab initio molecular dynamics (AIMD) calculation. This study provides a new guided strategy for developing and preparing carbonous materials to enhance the NRR performance experimentally.