Solvent‐Driven Modulation of Covalent‐Organic Framework Nano‐Architectures for Photothermal‐Catalytic Biomass Valorization and Hydrogen Peroxide Production

ABSTRACT The modulation of three‐dimensional (3D) covalent‐organic frameworks (COFs) into multifunctional nano‐architectures is highly desirable for their extended applications yet still challenging in both material design and morphology investigation. Here, we have designed a functional 3D COF (DPP‐TAM‐COF) and successfully modulated it into diverse nano‐architectures, including nano‐ring, hollow‐sphere, and nano‐urchin, through a solvent‐driven tuning strategy. The produced nano‐architectures possess bifunctional groups, well‐tuned morphology, high porosity, and photothermal properties that can be applied in efficient photothermal biomass valorization coupled with hydrogen peroxide production. Specifically, they can realize the furfuryl alcohol conversion into furoic acid with an optimal generation efficiency of 39.0 mmol/g coupled with the efficient hydrogen peroxide production, which is superior to the majority of reported materials. Based on various characterizations and theoretical calculations, the functions of nano‐architectures and bifunctional groups have been validated in the coupling reaction. Aiming at extending the application regimes of 3D COFs, this work might give new insights into the structure or morphology study of 3D COFs.