Formic Acid-Assisted Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N-Doped Mesoporous Carbon.
Formic Acid-Assisted Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N-Doped Mesoporous Carbon.
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DOI：
10.1002/anie.202012816
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发表时间：
2021-03-15
期刊：
影响因子：
--
通讯作者：
Peng B
中科院分区：
文献类型：
--
作者：
Hu B;Warczinski L;Li X;Lu M;Bitzer J;Heidelmann M;Eckhard T;Fu Q;Schulwitz J;Merko M;Li M;Kleist W;Hättig C;Muhler M;Peng B
生物质衍生的5-羟甲基糠醛（HMF）被认为是生产2，5-二甲基呋喃（DMF）作为潜在液体运输燃料的最有前途的平台化学品之一。制备了负载在含N和不含N的介孔碳材料上的Pd纳米颗粒，对其进行了表征，并在温和的反应条件下将其应用于HMF氢解为DMF。在甲酸（FA）和H2存在下，在Pd/NMC上在2小时内实现HMF向DMF的定量转化。 反应机理，特别是FA的多重作用，通过不同的氢源，添加剂和底物以及通过应用原位ATR-IR光谱进行详细的比较研究来探索。FA的主要作用是通过FA在C-OH基团上的质子化将主要反应途径从醛基的氢化转移到羟甲基的氢解，降低C-O键断裂的活化势垒，从而显着提高反应速率。XPS结果和DFT计算表明，Pd 2+物种与吡啶类N原子的相互作用显著增强了FA存在下C−OH键的选择性氢解，这是由于它们具有较高的FA活化和H−稳定能力。在甲酸和H2存在下，在双功能Pd/NMC催化剂上，在2 h内实现HMF向DMF的定量转化。 实验研究和密度泛函理论计算表明，甲酸显着提高反应速率和转移的主要反应途径从氢化的醛基的羟甲基基团通过其质子化的氢解。
Biomass‐derived 5‐hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5‐dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N‐containing and N‐free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR‐IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C‐OH group, lowering the activation barrier of the C−O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd2+ species interacting with pyridine‐like N atoms significantly enhance the selective hydrogenolysis of the C−OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H−. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid and H2 over the bifunctional Pd/NMC catalyst within 2 h. Experimental investigation and DFT calculation revealed that formic acid significantly enhances the reaction rate and shifts the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via its protonation.
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影响因子：
7.3
作者：
Bailon-Garcia, Esther;Carrasco-Marin, Francisco;Maldonado-Hodar, Francisco J.
通讯作者：
Maldonado-Hodar, Francisco J.
影响因子：
15
作者：
Graciani, Jesus;Nambu, Akira;Sanz, Javier Fdez.
通讯作者：
Sanz, Javier Fdez.
5-羟甲基糠醛和乙烯的综合转化用于生产可再生对二甲苯
影响因子：
23.5
作者：
Tao, Lei;Yan, Tian-Hao;Cao, Yong
通讯作者：
Cao, Yong
影响因子：
16.6
作者：
Du, Xian-Long;He, Lin;Fan, Kang-Nian
通讯作者：
Fan, Kang-Nian
影响因子：
7.3
作者：
He, Jiayue;Lu, Lu;Lercher, Johannes A.
通讯作者：
Lercher, Johannes A.