| 题名 | 催化转化5-羟甲基糠醛（HMF）制备呋喃衍生物 |
| 作者 | 苗珍珍 |
| 学位类别 | 博士 |
| 答辩日期 | 2015-04 |
| 授予单位 | 中国科学院研究生院 |
| 授予地点 | 中国科学院长春应用化学研究所 |
| 导师 | 杨向光 |
| 关键词 | 5-羟甲基糠醛 Cannizzaro反应 催化氧化 呋喃衍生物 表面修饰 |
| 中文摘要 | 利用可再生的生物质资源制备精细化学品意义重大。5-羟甲基糠醛（HMF）是糖类在酸催化下的脱水产物，是一种重要的生物质衍生物，受到很大的关注。HMF可以通过氧化、氢化等反应转化成2,5-呋喃二甲醛（DFF）、2,5-二羟甲基呋喃（BHMF）、5-羟甲基-2-呋喃甲酸（HFCA）和2,5-呋喃二甲酸（FDCA）等呋喃衍生物，它们可作为高分子聚合物的单体，也可以用于制备多种精细化学品。目前，开发高效的、环境友好的催化体系用于催化转化HMF制备呋喃衍生物是研究的热点。 使用柠檬酸溶胶凝胶法对CeO2进行Bi的掺杂改性，得到的固溶体存在大量的氧空位缺陷。Ce1-xBixO2-δ（0.08≤x≤0.5）可以有效催化 HMF在碱性水溶液中转化生成BHMF和HFCA，反应20分钟后，HMF转化率达97%。这是首次发现的非贵金属氧化物催化的HMF的Cannizzaro反应且Bi的掺杂具有特异性。Ce1-xBixO2-δ（x≤0.2）上负载Au后，得到的催化剂可以有效催化HMF氧化生成FDCA。使用Au/Ce0.9Bi0.1O2-δ催化剂，65℃下反应2小时，FDCA的收率大于99%。 制备了PVP稳定的Pt溶胶并负载在Ce1-xBixO2-δ上用于催化HMF转化。Pt/Ce0.8Bi0.2O2-δ催化剂表现了优异的催化氧化活性，室温下反应30分钟，FDCA收率高达98%。这是首次发现的铈基载体负载的Pt催化剂高效催化醇的氧化反应。Bi的存在使Ce0.8Bi0.2O2-δ具有优异的低温活性氧的能力，在催化氧化过程中，Pt和Ce0.8Bi0.2O2-δ发挥各自特定的功能，它们的作用很好的结合，实现高效的催化醇和醛的氧化。 不同的Bi系氧化物负载的Pt催化剂都表现出优异的催化HMF氧化的性能，使用Pt/Bi2W3O12催化剂时，室温下反应仅15分钟，HMF完全转化，FDCA的收率高达99%。反应体系中碱的浓度、氧压、反应温度和催化剂的用量对产物分布都有较大影响。 Au/LaMO3（M=Cr，Mn，Fe，Co，Ni）催化剂在高温、高氧压条件下可以催化HMF氧化制备HFCA和FDCA。在室温、大气环境下反应，Au/LaMnO3可以有效催化HMF发生Cannizzaro反应。对LaMnO3进行Zn掺杂后，得到的Au/LaMn0.9Zn0.1O3在室温、大气环境下高效催化HMF的转化，反应仅5分钟，HMF完全转化，产生等量的Cannizzaro反应产物HFCA和BHMF。 以SiO2@Au为模型催化剂，考察了不同处理条件对其催化环己烷选择氧化的活性影响。对SiO2@Au直接烷基化疏水处理造成催化活性的降低，包硅后再疏水处理得到的SiO2@Au@SiO2-s催化剂的催化活性明显提高，150℃下反应3小时，环己烷的转化率达13%，环己醇和环己酮的总选择性近80%。 |
| 英文摘要 | With the continuous consumption of fossil resources, it is of great importance to exploit and utilize renewable biomass resources for preparation of bulk and fine chemicals. 5-Hydroxymethylfurfural (HMF), which can be obtained from dehydration of glucose or fructose under the catalyzing of acid, is a compelling platform chemical for the production of 2,5-diformylfuran (DFF), 2,5-bishydroxymethylfuran (BHMF), 5-hydroxymethyl-2-furancarboxylic acid (HFCA) and 2,5-furandicarboxylic acid (FDCA). These stuffs have been regarded as promising monomers for preparing resins, polymers and fine chemicals. The development of highly efficient, environmental-friendly catalytic system for the preparation of furan-based materials from HMF is a key research field nowadays. Porous Bi-doped ceria was prepared by the citrate method, and there existed large amount of oxygen vacancies in the obtained Ce1?xBixO2?δ solid solution. In the presence of O2, Ce1?xBixO2?δ (0.08 ≤ x ≤ 0.5) efficiently catalyzed the conversion of HMF to HFCA and BHMF in alkaline aqueous solution without degradation of HMF. A 97% conversion of HMF was achieved only after 20 min. The excellent catalytic activity was attributed to the oxygen activation and hydride transfer enhanced by Bi doping and the large amount of oxygen vacancies. After Au nanoparticles (NPs) were supported on Ce1?xBixO2?δ (x ≤ 0.2), the presence of Auδ+ facilitated the activation of the C-H bond in the hydroxymethyl group and then the production of FDCA as an end product, inhibiting the generation of BHMF. When performing the reaction at 65 °C, a >99% yield of FDCA was obtained after 2 h over the Au/Ce0.9Bi0.1O2?δ catalyst. The oxidation of HMF to FDCA was efficiently catalyzed when PVP stabilized Pt NPs were supported onto a Ce0.8Bi0.2O2?δ solid solution. 98% yield of FDCA was achieved within 30 min at room temperature and the catalyst was reused five times without much loss of FDCA selectivity. It is the first report on the oxidation of HMF, an alcohol and an aldehyde, effectively catalyzed by a ceria-based material supported Pt catalyst. The individual properties of the Pt NPs and the ceria-based support were retained and not affected after their combination. The superior oxygen activation ability of the Bi-doped ceria thoroughly changed the performance of the ceria supported Pt catalyst. The specific functions of Pt NPs and Bi-containing ceria were well incorporated during the catalytic oxidation cycle, leading to the generation of the highly efficient Pt/Ce0.8Bi0.2O2?δ catalyst for the oxidation of alcohol group and aldehyde group at room temperature. A series of Bi-contained oxide supported Pt catalyst were prepared and was evaluated for the selective oxidation of HMF to FDCA. All the catalysts showed excellent catalytic activities. When using Pt/Bi2W3O12 catalyst, a 100% conversion of HMF and a 99% yield of FDCA were obtained only after 15 min at room temperature. The effect of the reaction parameters on the product distribution was also investigated, such as amount of base, oxygen pressure, temperature and the usage amount of catalyst. When performing the reaction at high temperature and high oxygen pressure, the prepared Au/LaMO3 (M = Cr, Mn, Fe, Co, Ni) could catalyze the oxidation of HMF to HFCA and FDCA. When it reaction at room temperature and air atmosphere, the Au/LaMnO3 efficiently catalyzed the Cannizzarro reaction of HMF, and the catalytic activity was highly enhanced after doping 10mol% Zn in the Au/LaMnO3. With the presence of Au/LaMn0.9Zn0.1O3, HMF was totally converted only after reaction for 5 min, the Cannizzarro reaction products BHMF and HFCA were obtained equally. Liquid-phase selective oxidation of cyclohexane is a very important reaction in the industry. The effect of the treatment conditions on the catalytic activity towards cyclohexane oxidation was investigated using the model catalyst, SiO2@Au. The hydrophobic treatment reduced the catalytic |
| 语种 | 中文 |
| 公开日期 | 2016-05-03 |
| 内容类型 | 学位论文 |
| 源URL | [http://ir.ciac.jl.cn/handle/322003/64484]  |
| 专题 | 长春应用化学研究所_长春应用化学研究所知识产出_学位论文 |
| 推荐引用方式 GB/T 7714 | 苗珍珍. 催化转化5-羟甲基糠醛（HMF）制备呋喃衍生物[D]. 中国科学院长春应用化学研究所. 中国科学院研究生院. 2015. |
| 个性服务 |
| 查看访问统计 |
| 相关权益政策 |
| 暂无数据 |
| 收藏/分享 |
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。
修改评论