Bi/N‐Doped Porous Carbon with Dominant Pyridinic N Sites to Facilitate Low Energy Pathways for CO ₂ to Formate Conversion

Abstract The electrochemical conversion of CO ₂ to value‐added products is perceived to be a promising strategy for mitigating CO ₂ emissions and promoting environmental sustainability. This work reports the preparation of a series of N‐doped porous carbons containing ultrafine dispersions of bismuth using a facile metal‐organic framework‐assisted strategy. The Bi/NC catalyst with optimal bismuth loading (24.8 wt.%) demonstrates appreciable catalytic activity toward electrochemical CO ₂ reduction reaction (eCO ₂ RR) by the effective conversion of CO ₂ to formate with a more positive onset potential of −0.6 V (vs RHE) and high electrochemically active surface area. As a result, the catalyst possesses formate faradaic efficiency of 91% at −0.8 V (vs RHE) with a long‐term stability of 24 h in 0.5 m KHCO ₃ solution. The remarkable catalytic activity of the catalyst is ascribed to the combined effect of enhanced metallic active sites and the enhanced mass transport facilitated via micro‐meso porous carbon matrix containing dominant pyridinic N sites. Notably, DFT calculations reveal that pyridinic N‐ doping in a carbon matrix containing bismuth nanoparticles lowers the energy barrier of ^* OCHO formation and suppresses the competitive hydrogen evolution reaction.