Dual atomic catalysts from COF-derived carbon for CO2RR by suppressing HER through synergistic effects

The electrochemical carbon dioxide reduction reaction (CO2RR) for high-value-added products is a promising strategy to tackle excessive CO2 emissions. However, the activity of and selectivity for catalysts for CO2RR still need to be improved because of the competing reaction (hydrogen evolution reaction). In this study, for the first time, we have demonstrated dual atomic catalytic sites for CO2RR from a core-shell hybrid of the covalent-organic framework and the metal-organic framework. Due to abundant dual atomic sites (with CoN4O and ZnN4 of 2.47 and 11.05 wt.%, respectively) on hollow carbon, the catalyst promoted catalysis of CO2RR, with the highest Faradic efficiency for CO of 92.6% at -0.8 V and a turnover frequency value of 1370.24 h(-1) at -1.0 V. More importantly, the activity and selectivity of the catalyst were well retained for 30 h. The theoretical calculation further revealed that CoN4O was the main site for CO2RR, and the activity of and selectivity for Zn sites were also improved because of the synergetic roles.

Automated summary

In this study, we demonstrated the role of dual atomic catalytic sites in the electrochemical carbon dioxide reduction reaction (CO2RR) using a core-shell hybrid of the covalent-organic framework and the metal-organic framework. With abundant dual atomic sites (CoN4O and ZnN4) on hollow carbon, the catalyst exhibited high activity and selectivity for CO2RR, achieving a Faradic efficiency for CO of 92.6% at -0.8 V and a turnover frequency value of 1370.24 h^(-1) at -1.0 V. The catalyst also showed excellent stability for 30 hours. Theoretical calculations revealed the main role of CoN4O in CO2RR and improved activity and selectivity of Zn sites due to synergistic effects.