Co-porphyrin-based metal-organic framework for light-driven efficient green conversion of CO2 and epoxides

Abstract

The cyclization of CO₂ with epoxides to produce cyclic carbonate compounds represents a significant avenue for achieving CO₂ emission reduction and optimizing resource utilization. However, this process typically demands rigorous reaction conditions. In this study, we have successfully constructed three layered columnar porphyrin metal–organic frameworks with double interpenetrated network configurations, denoted as Co-PMOFs 1–3, which have excellent photosensitivity, effective CO₂ adsorption, regularly ordered pore structures, and high-density monodispersed catalytically active centers by employing solvent-modulated and ligand-modulated construction strategies. Co-PMOFs 1–3 exhibit excellent catalytic performance in the traditional thermally-driven CO₂ cycloaddition reaction with epoxides under solvent-free conditions (75 °C and 1 bar). Notably, Co-PMOF 3 exhibits a wider pore environment, ensuring sustained efficient catalytic activity for larger-sized reaction substrates.Significantly, the incorporation of porphyrin and anthracene motifs enables the harnessing of solar energy, thereby enhancing the reaction efficiency under ambient temperature and pressure conditions. The majority of epoxides can be nearly completely transformed (> 99 %) into cyclic carbonates within a concise timeframe of 6 h. This investigation not only presents a distinguished class of MOFs-catalysts for CO₂ cyclization reactions but also imparts novel insights for the rational design of high-quality photocatalysts in future heterogeneous catalytic processes.