Metal‐Free Nitrogen‐Doped Mesoporous Carbon for Electroreduction of CO2 to Ethanol

CO₂ electroreduction is a promising technique for satisfying both renewable energy storage and a negative carbon cycle. However, it remains a challenge to convert CO₂ into C2 products with high efficiency and selectivity. Herein, we report a nitrogen‐doped ordered cylindrical mesoporous carbon as a robust metal‐free catalyst for CO₂ electroreduction, enabling the efficient production of ethanol with nearly 100 % selectivity and high faradaic efficiency of 77 % at −0.56 V versus the reversible hydrogen electrode. Experiments and density functional theory calculations demonstrate that the synergetic effect of the nitrogen heteroatoms and the cylindrical channel configurations facilitate the dimerization of key CO* intermediates and the subsequent proton–electron transfers, resulting in superior electrocatalytic performance for synthesizing ethanol from CO₂.