摘要：The use of carbon‐based materials is an appealing strategy to solve the issue of excessive CO_(2) emis‐*** particular,metal‐free nitrogen‐doped carbon materials(mf‐nCs)have the advantages of convenient synthesis,cost‐effectiveness,and high conductivity and are ideal electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR).However,the unclear identification of the active n sites and the low intrinsic activity of mf‐nCs hinder the further development of high‐performance CO_(2)RR electrocat‐*** precise control over the synthesis of mf‐nC catalysts with well‐defined active n‐species sites is still *** this end,we adopted a facile synthesis method to construct a set of mf‐nCs as robust catalysts for CO_(2)*** resulting best‐performing catalyst obtained a Far‐adaic efficiency of CO of approximately 90%at−0.55 V(*** hydrogen electrode)and good *** electrocatalytic performance and in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy measurements collectively revealed that graphitic and pyridinic n can synergistically adsorb CO_(2) and H_(2)O and thus promote CO_(2) activation and protonation.