A Conjugated Neodymium‐Based Metal−Organic Framework for Efficient Photocatalytic CO 2 Cycloaddition

The photocatalytic cycloaddition of CO 2 with epoxides offers a sustainable approach for CO 2 fixation and value‐added carbonate synthesis, yet developing well‐defined photocatalysts that integrate narrow bandgap, abundant active sites, and strong CO 2 enrichment ability remains challenging. Herein, a new conjugated metal−organic framework (MOF) using hexahydroxytriphenylene as linkers and hexanuclear [Nd 6 ( μ 6 ‐CO 3 )O 12 ] 8− as inorganic nodes is constructed. The obtained FDM‐154 possesses interconnected 13.6 Å pores and a surface area of 532 m 2 g −1 , enabling efficient CO 2 enrichment (28.5 cm 3 g −1 ). Furthermore, FDM‐154 features a narrow optical bandgap of 1.12 eV, which facilitates photogenerated charge separation under visible light. Additionally, the MOF backbone is decorated with dense photoactive organic linkers and Nd 3+ Lewis acid sites that serve as active centers to efficiently activate both CO 2 and epoxide substrates during the photocatalytic process. FDM‐154 photocatalyst achieves high yield for CO 2 cycloaddition with epichlorohydrin under mild conditions, resulting from the combined effect of its suitable band structure, accessible active sites, and pore confinement effect.