Designing dual-atom cobalt catalysts anchored on amino-functionalized MOFs for efficient CO2 photoreduction†

Abstract

Unlocking the potential of sustainable fuel production through the development of highly efficient CO₂ reduction catalysts under visible light irradiation remains an ongoing challenge. Herein, we report a strategically designed Zr-based metal–organic framework (MOF) photocatalyst, incorporating binuclear cobalt complexes as catalytic sites for effective CO₂ reduction. Impressively, our Co₂-MOF(–NH₂) catalyst showcased a CO yield of 2.44 mmol g_Co⁻¹ h⁻¹, outperforming its mononuclear counterpart Co-MOF(–NH₂) (0.23 mmol g_Co⁻¹ h⁻¹) by 10.5 times, underscoring the exceptional catalytic capabilities of the dual-atom catalyst. A combination of experimental findings and Density Functional Theory (DFT) calculations unveiled the synergistic catalytic effect between the two Co sites and the heightened light absorption attributed to the incorporation of the amino group. Notably, such characteristics are evocative of cooperative catalysis observed in biological enzyme systems. This study highlights a pioneering, bioinspired approach to designing efficient dual-atom MOF photocatalysts for CO₂ reduction, offering significant implications for the future of sustainable energy production.