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.