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Selective Oxidation of 5 Hydroxymethylfurfural to 2,5- Diformylfuran by Visible Light-Driven Photocatalysis over In Situ Substrate-Sensitized Titania



Solar energy-driven processes for biomass valorization are priority for the growing industrialized society. To address this challenge, efficient visible light-active photocatalyst for the selective oxidation of biomass-derived platform chemical is highly desirable. Herein, selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5- diformylfuran (DFF) is achieved by visible light-driven photocatalysis over titania. Pristine titania is photocatalytically inactive under visible light, an unconventional approach is employed for the visible light (λ =515 nm) sensitization of titania via a formation of a visible light absorbing complex of HMF (substrate) on the titania surface. Surface-complexation of HMF on titania mediate ligand-to-metal charge transfer (LMCT) under visible light, which efficiently catalyzes the oxidation of HMF to DFF. A high DFF selectivity of 87% is achieved with 59% HMF conversion after 4 hours of illumination. Whereas, the apparent quantum yield obtained for DFF production is calculated to be 6.3%. It is proposed that the dissociative interaction of hydroxyl groups of HMF and the titania surface is responsible for the surface-complex formation. When the hydroxyl groups of titania are modified via surface-fluorination or calcination the oxidation of HMF is inhibited under visible light, signifying that hydroxyl groups are decisive for photocatalytic activity.

Selective Oxidation of 5 Hydroxymethylfurfural to 2,5- Diformylfuran by Visible Light-Driven Photocatalysis over In Situ Substrate-Sensitized Titania

A. Khan, M. Goepel, A. Kubas, D. Łomot, W. Lisowski, D. Lisovytskiy, A. Nowicka, J.C. Colmenares, and R. Gläser. ChemSusChem, 14 (2021) 13511362. OPEN ACCESS!!!


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