Atomically Dispersed Dual-Metal-Site Catalysts Boost the CO ₂ Cycloaddition Reaction with Epoxides

Seeking low-cost catalysts with enhanced catalytic performance is a promising strategy to address the challenges of the cycloaddition reaction of CO 2 with epoxides under mild conditions. Herein, dual-metal-site catalysts derived from ZIF-8 via a facile pyrolysis strategy have been exploited for the first time in a cycloaddition reaction. In particular, the Mn–N/Zn–N dual-metal-site catalyst achieved 100% conversion and 100% selectivity under optimal conditions, surpassing the most reported noble metal catalysts. Notably, the catalytic activity of the Mn–N/Zn–N dual-metal-site catalyst is higher than that of the single-metal-site Zn–N catalyst under the same conditions. Density functional theory calculations reveal that, compared with the Fe–N/Zn–N and Zn–N catalysts, the Mn–N/Zn–N dual-metal-site catalyst has a lower Gibbs free energy barrier of the rate-determining step, which accounts for the higher catalytic activity toward the cycloaddition reaction of CO 2 with epoxides. We believe that this work will expand the array of dual-metal-sitecatalyst options available for the conversion of CO 2 into high-value chemicals.