Molecular Evidences for Metallic Cobalt Boosting CO2 Electroreduction on Pyridinic Nitrogen.

Nitrogen-doped carbon materials (N-Cs) are emerging as low-cost metal-free electrocatalysts for electrochemical CO 2 reduction reaction (CO 2 RR), although the activities are still unsatisfactory and the genuine active site thereof is still arguable. We herein demonstrate that CO 2 RR to CO preferentially take place on pyridinic N rather than pyrrolic N using phthalocyanine (Pc) and porphyrin with well-defined N-C configurations as molecular model catalysts. Systematic experiments and theoretic calculations further discover 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 the new insights into the CO 2 RR on N-Cs, which may guide the exploration of cost-effective electrocatalysts for efficient CO 2 RR.

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