2D MOF/COF Heterojunction for Efficient Photothermal Synergistic Catalysis of CO ₂ Reduction

Abstract Photothermal synergistic catalysis of carbon dioxide (CO ₂ ) reduction by combining the advantages of photocatalysis and thermocatalysis is an effective strategy for enhancing the efficiency of solar‐to‐fuel conversion. However, it is still a great challenge to integrate the high photothermal effect and charge separation efficiency simultaneously in one system. Herein, a type of bonded 2D Metal organic framework (MOF)/Covalent organic framework (COF) heterostructure with the same linker is constructed for efficient photothermal synergistic catalysis of CO ₂ reduction. In this system, an S‐scheme heterojunction interface is formed between the MOF (CAT‐1) and COF‐316 through planar conjugated molecules, which facilitates the separation of photogenerated charge carriers. CAT‐1 serves as a photoinduced self‐heating component and simultaneously provides active metal sites for CO ₂ reduction, enabling efficient photothermal conversion under visible‐near‐infrared light. As a result, a series of CAT‐1/COF‐316 composites delivered enhanced photothermal catalytic activity for CO ₂ reduction without adding additional photosensitizers, with the optimal CO production rate of 263.63 µmol g ⁻¹ h ⁻¹ . Detailed control experiments and density functional theory (DFT) calculations confirm that the superior photothermal catalytic CO ₂ reduction performance of CAT‐1/COF‐316 is attributed to the synergistic effect of photo‐thermal processes and highly improved charge separation. The present work provides a potential strategy for developing highly‐efficient photothermal catalysts in artificial photosynthesis.