Aerobic oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran using manganese dioxide with different crystal structures: A comparative study | IDCSA, NCHU

Aerobic oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran using manganese dioxide with different crystal structures: A comparative study 2021-02-15

Recycling Agriculture: Rising value of Agricultural Waste【Department of Environmental Engineering / Lin, Kun-Yirew / Distinguished Professor】
循環農業：農業廢棄物高價值化【環境工程學系/林坤儀特聘教授】

論文篇名	英文：Aerobic oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran using manganese dioxide with different crystal structures: A comparative study 中文：使用不同晶體結構的二氧化錳將 5-羥甲基糠醛有氧氧化為 2,5-二甲酰基呋喃：比較研究
期刊名稱	Journal of Colloid and Interface Science
發表年份,卷數,起迄頁數	2021, 592, 416
作者	Lin, Kun-Yi Andrew(林坤儀); Oh, Wen-Da; Zheng, Meng-Wei; Kwon, Eilhann; Lee, Jechan; Lin, Jia-Yin; Duan, Xiaoguang; Ghanbari, Farshid
DOI	10.1016/j.jcis.2021.02.030
中文摘要	使用 O₂ 氣體將 5-羥甲基糠醛 (HMF) 有氧氧化為 2,5-二甲酰基呋喃 (DFF) 代表了木質纖維素化合物價值化的可持續方法。由於二氧化錳 (MnO₂) 被證實是一種有用的氧化催化劑，並且存在多種 MnO₂ 晶型，因此探索 MnO₂ 的晶體結構如何影響其物理/化學性質至關重要，而這反過來又決定了 MnO₂ 晶體的催化活性用於 HMF 氧化為 DFF。特別是，製備了六種 MnO2 晶體，α-MnO₂、β-MnO₂、γ-MnO₂、δ-MnO₂、ε-MnO₂ 和 λ-MnO₂，並研究了它們對 HMF 氧化成 DFF 的催化活性。由於具有不同的形態和晶體結構，這些 MnO₂ 晶體具有非常不同的表面化學、氧化還原能力和結構特性，使這些 MnO₂ 對 HMF 轉化表現出不同的催化活性。特別是，β-MnO₂ 可以比其他 MnO₂ 晶體產生更高的單位表面積 DFF。 β-MnO₂ 可以達到最高的 C_HMF = 99% 和 Y_DFF = 97%，遠高於文獻報導的值，可能是因為與其他 MnO₂ 晶體相比，β-MnO₂ 的表面反應性似乎最高。特別是，β-MnO₂ 在 5 次可重複使用性測試循環中的 Y_DFF > 90%，並保持其晶體結構，揭示了其將 HMF 有氧氧化為 DFF 的有利特徵。通過這項研究，闡明了不同晶型 MnO₂ 的形貌、表面化學和催化活性之間的關係，為 MnO₂ 基材料的設計、應用和開發提供科學見解，用於生物衍生分子的有氧氧化以實現增值產品。
英文摘要	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.
發表成果與本中心研究主題相關性	透過本研究可進一步建立可用於循環農業中將農業廢棄物及衍生物轉換成價值附加產物之技術。