Molecular Evidence for Metallic Cobalt Boosting CO 2 Electroreduction on Pyridinic Nitrogen

Nitrogen‐doped carbon materials (N‐C mat ) are emerging as low‐cost metal‐free electrocatalysts for the electrochemical CO 2 reduction reaction (CO 2 RR), although the activities are still unsatisfactory and the genuine active site is still under debate. We demonstrate that the CO 2 RR to CO preferentially takes place on pyridinic N rather than pyrrolic N using phthalocyanine (Pc) and porphyrin with well‐defined N‐C mat configurations as molecular model catalysts. Systematic experiments and theoretic calculations further reveal that the CO 2 RR performance on pyridinic N can be significantly boosted by electronic modulation from in‐situ‐generated metallic Co nanoparticles. By introducing Co nanoparticles, Co@Pc/C can achieve a Faradaic efficiency of 84 % and CO current density of 28 mA cm −2 at −0.9 V, which are 18 and 47 times higher than Pc/C without Co, respectively. These findings provide new insights into the CO 2 RR on N‐C mat , which may guide the exploration of cost‐effective electrocatalysts for efficient CO 2 reduction.