High-efficient and recoverable Mo72V30@Fe3O4/C catalyst for oxidation of hydroxyfurfural
High-efficient and recoverable Mo72V30@Fe3O4/C catalyst for oxidation of hydroxyfurfural
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DOI：
10.1016/j.fuel.2022.126050
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发表时间：
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期刊：
影响因子：
7.4
通讯作者：
Mengdi Gong;Xin‐Yu Wang;Mu-Qin Li;Wenjun Mu;Yundong Cao;Hong Liu;Yuexin Lv;Xin-Hua Qi;
中科院分区：
文献类型：
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作者：
Mengdi Gong;Xin‐Yu Wang;Mu-Qin Li;Wenjun Mu;Yundong Cao;Hong Liu;Yuexin Lv;Xin-Hua Qi;
开发高效、高选择性、可循环利用的多金属氧酸酯（POM）基催化剂是5-羟甲基糠醛（HMF）氧化反应的一大挑战。本文设计了MIL-88A（Fe）衍生的Fe3O4/C作为高效载体诱捕keplerte型POM，形成Mo72V30@Fe3O4/C复合催化剂。由于Fe3O4/C框架的限制和协同作用，与其他已报道的催化剂相比，Mo72V30@Fe3O4/C在HMF的有氧氧化中表现出最高的催化活性和选择性，转化率为99.4%，对2,5-二甲酰呋喃（DFF）的选择性为100%。Mo72V30@Fe3O4/C催化剂经过10次循环后仍具有较高的活性。提出了一种可能的协同催化机制，Mo72V30@Fe3O4/C通过质子耦合电子转移（PCET）过程将HMF氧化为DFF，表明Mo72V30@Fe3O4/C中的多金属中心协同促进了该反应。这项工作不仅为生物质转化提供了一个巨大的基于POM的催化剂，而且为生物质氧化催化剂的设计突出了多金属活性中心的概念。
It is a great challenge to develop recyclable polyoxometalate (POM) based catalysts with high efficiency and selectivity in oxidation of 5-hydroxymethylfurfural (HMF). In this paper, MIL-88A(Fe) derived Fe3O4/C is designed as an efficient carrier to entrap Keplerate-type POM and form Mo72V30@Fe3O4/C composite catalyst. Due to the confined and synergistic effect of Fe3O4/C framework, as compared to other reported catalysts, Mo72V30@Fe3O4/C exhibits the highest catalytic activity and selectivity in aerobic oxidation of HMF with a 99.4 % conversion and a 100 % selectivity to 2,5-diformylfuran (DFF). The Mo72V30@Fe3O4/C catalyst still shows a high activity even after ten cycles. A possible synergistic catalytic mechanism is proposed that Mo72V30@Fe3O4/C oxidizes HMF to DFF through a proton coupled electron transfer (PCET) process indicating the polymetallic center in Mo72V30@Fe3O4/C synergistically promotes this reaction. This work not only provides a giant POM based catalyst in biomass conversion, but also highlights a polymetallic active center concept for the design of biomass oxidation catalyst.