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5-Hydroxymethylfurfural Oxidation to Maleic Acid by O2 over Graphene Oxide Supported Vanadium: Solvent Effects and Reaction Mechanism
Chemical Engineering Journal ( IF 13.3 ) Pub Date : 2020-01-23 , DOI: 10.1016/j.cej.2020.124187
Lin Chai , Xianglin Hou , Xiaojing Cui , Hongyan Li , Ning Zhang , Hui Zhang , Chengmeng Chen , Yingxiong Wang , Tiansheng Deng

Oxidation of 5-hydroxymethylfurfural (HMF) with molecular oxygen to maleic acid (MAc) was performed on graphene oxide (V-GO) supported vanadium composite. The solvent effects (γ-valerolatctone (GVL), acetic acid and H2O) on the reaction were investigated by combing the characterizations of X-ray Photoelectron Spectroscopy (XPS), 13C and 1H Nuclear Magnetic Resonance (13C-NMR and 1H-NMR), Inductive Coupled Plasma Emission Spectrometer (ICP), and Elemental Analysis (EA), and kinetic studies. GVL was the most efficient solvent with the highest yield of MAc, while acetic acid and H2O benefited the C-C cleavage, giving more formic acid (FAc) than GVL. These variation in the solvent effects originated from the different ability of solvents to convert HMF molecules and 5-hydroxyl-2(5H)-furanone (HF) intermediate. Besides, the protons (H+) in graphene oxide were identified to promote HMF oxidation to MAc, whereas the added NaHCO3 caused the catalyst deactivation. By combing the fabrication of model catalyst and XPS analysis, this negative effect of NaHCO3 resulted from both the inhibition in the reduction of V5+→V4+ and/or V4+→V3+ and the loss in the H+ sites on the GO support caused by neutralization reaction. Furthermore, the reaction intermediates were identified by NMR. Oxidation of HMF to MAc was a two-step process, i.e., HMF oxidization to HF intermediate and its following oxidation to MAc. Both oxidation steps required the presence of vanadium and O2. A feasible path for HMF oxidation to MAc was proposed based on the NMR observations.



中文翻译:

O 2在氧化石墨烯负载的钒上O 2氧化5-羟甲基糠醛成马来酸:溶剂效应和反应机理

在氧化石墨烯(V-GO)负载的钒复合材料上,用分子氧将5-羟甲基糠醛(HMF)氧化为马来酸(MAc)。通过结合X射线光电子能谱(XPS),13 C和1 H核磁共振(13 C-NMR )的表征,研究了溶剂对反应的影响(γ-戊内酯(GVL),乙酸和H 2 O)。和1 H-NMR),电感耦合等离子体发射光谱仪(ICP),元素分析(EA)和动力学研究。GVL是MAc收率最高的最有效溶剂,而乙酸和H 2O有利于CC裂解,比GVL产生更多的甲酸(FAc)。溶剂作用的这些变化源于溶剂转化HMF分子和5-羟基-2(5H)-呋喃酮(HF)中间体的不同能力。此外,还发现氧化石墨烯中的质子(H +)可以促进HMF氧化成MAc,而添加的NaHCO 3则使催化剂失活。通过组合模型催化剂的制备和XPS分析,NaHCO 3的这种负面影响既是由于抑制了V 5+ →V 4+和/或V 4+ →V 3+的还原以及H +的损失中和反应引起GO载体上的位点。此外,反应中间体通过NMR鉴定。HMF氧化为MAc的过程分为两步,即HMF氧化为HF中间体及其随后的氧化为MAc。这两个氧化步骤都需要存在钒和O 2。基于NMR观察结果,提出了HMF氧化为MAc的可行途径。

更新日期:2020-01-24
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