Bifunctional Nitrogen and Cobalt Codoped Hollow Carbon for Electrochemical Syngas Production

Electrochemical conversion of CO₂ and H₂O into syngas is an attractive route to utilize green electricity. A competitive system economy demands development of cost-effective electrocatalyst with dual active sites for CO₂ reduction reaction (CO₂RR) and hydrogen evolution reaction (HER). Here, a single atom electrocatalyst derived from a metal-organic framework is proposed, in which Co single atoms and N functional groups function as atomic CO₂RR and HER active sites, respectively. The synthesis method is based on pyrolysis of ZnO@ZIF (zeolitic imidazolate framework). The excess in situ Zn evaporation effectively prevents Co single atoms (≈3.4 wt%) from aggregation and maintains appropriate Co/N ratio. The as-prepared electrocatalyst is featured with high graphitic degree of carbon support for rapid electron transport and sponge-like thin carbon shells with hierarchical pore system for facilitating active site exposure and mass transport. Therefore, the electrocatalyst exhibits a nearly 100% Faradic efficiency and a high formation rate of ≈425 mmol g^-1 h^-1 at 1.0 V with the gaseous product ratio (CO/H₂) approximating ideal 1/2. With the assistance of an extensive material characterization and density functional theory (DFT) calculations, it is identified that Co single atoms are uniformly coordinated in the form of Co-C₂N₂ moieties, and act as the major catalytic sites for CO₂ reduction.