Designing Photothermal Catalytic Systems in Multi-Component MOFs for Enhanced Conversion of Carbon Dioxide

Abstract

Combining catalytic centers with photothermal materials offers a promising approach for harnessing sunlight to catalyze diverse chemical reactions. Nevertheless, it is challenging to precisely design photothermal catalysts with well-defined photothermal and catalytic centers. In this work, we integrated photothermal units with Lewis and nucleophilic catalytic sites within a multi-component metal-organic framework (MOF) for enhanced conversion of CO2 to cyclic carbonates. We initially synthesized a Zr-MOF with tetrathiafulvalene (TTF)-based linkers (Zr-TTF), featuring accessible coordination sites to accommodate secondary linkers. Subsequently, a series of linkers bearing pyridinium iodide center (L1) and electron acceptor units, either tetrazine-based L2 or naphthalene diimide (NDI)-based L3, were sequentially installed into Zr-TTF, forming multi-component MOFs. Single-crystal to single-crystal transformation was realized throughout the post-synthetic modification, enabling the precise localization of the inserted linkers via single-crystal X-ray diffraction. Under light irradiation, the multi-component Zr-TTF-L1-L3 significantly enhances CO2 cycloaddition yield, highlighting the synergistic advantages of Lewis acidic Zr4+, nucleophilic iodide, and photothermal heating from the donor-acceptor (TTF-NDI) pairs.