Aerobic oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran using manganese dioxide with different crystal...

Aerobic oxidation of 5-Hydroxymethylfurfural (HMF) to 2,5-Diformylfuran (DFF) using O₂ gas represents a sustainable approach for valorization of lignocellulosic compounds. As manganese dioxide (MnO₂) is validated as a useful oxidation catalyst and many crystalline forms of MnO₂ exist, it is critical to explore how the crystalline structures of MnO₂ influence their physical/chemical properties, which, in turn, determine catalytic activities of MnO₂ crystals for HMF oxidation to DFF. In particular, six MnO₂ crystals, α-MnO₂, β-MnO₂, γ-MnO₂, δ-MnO₂, ε-MnO₂, and λ-MnO₂ are prepared and investigated for their catalytic activities for HMF oxidation to DFF. With different morphologies and crystalline structures, these MnO₂ crystals possess very distinct surficial chemistry, redox capabilities, and textural properties, making these MnO₂ exhibit different catalytic activities towards HMF conversion. Especially, β-MnO₂ can produce much higher DFF per surface area than other MnO₂ crystals. β-MnO₂ could achieve the highest C_HMF = 99% and Y_DFF = 97%, which are much higher than the reported values in literature, possibly because the surficial reactivity of β-MnO₂ appears to be highest in comparison to other MnO₂ crystals. Especially, β-MnO₂ could exhibit Y_DFF > 90% over 5 cycles of reusability test, and maintain its crystalline structure, revealing its advantageous feature for aerobic oxidation of HMF to DFF. Through this study, the relationship between morphology, surface chemistry, and catalytic activity of MnO₂ with different crystal forms is elucidated for providing scientific insights into design, application and development of MnO₂-based materials for aerobic oxidation of bio-derived molecules to value-added products.