Al基催化剂作用下葡萄糖转化为呋喃类化合物反应机理的理论研究

Most of the carbon-based compounds currently manufactures by the chemical industry are derived from petroleum. The rising cost and dwindling supply of oil have been focusing attention on possible routes to making chemicals, fuels, and solvents from biomass instead. The utlization of glucose, as the renewably biomass, for the production of furans has become of growing interest. The Al-containing catalysts are responsible for the glucose conversion into 5-hydroxymethylfurfural (HMF), while the V, Mo, W-containing catalysts are responsible for the oxidation of HMF. The high accurate quantum methods are explored to investigate the catalytic reaction mechanisms of glucose conversion into furans on Al-containing homogeneous catalysts, and Al, V, Mo, and V-containing heteropolyacid and zeolite catalysts in several different solvents. The contents of the present investigation are as follows: (a) to acquire the determining transition state and intermediate by the calculation of the catalytic turnover frequency (TOF), (b) to obtain the effect of sovent on the catalytical efficiency of Al-containing catalyst, (c) to accumulate the thermodynamic and kinetic data , (d) to provide insight into the intrinsic relationship of Al-containing catalyst on the structure with property, (e) to design the model of the Al-containing multifunctional heteropolyacid and zeolite catalyst, and (f) to predict the thermodynamic and kinetic data of the designed catalytic reactions. The present investigation is helpful to the understand the nature of catalytic reactions, and design and develop the green and effective catalysts for glucose conversion into furans. It is very important to explore the rule of the complicated system kinetics, to utilize reasonably resource, to control, and remove envirnomeantal pollution, to innovate the low-carbon technology, and to bring into effect on the continuous development of economy.

生物质主要成分纤维素水解可得到葡萄糖，葡萄糖催化转化得到的呋喃类化合物是连接生物质化学和石油化工的很重要的平台化合物。以此为背景，采用高精度的量子化学和分子力场相结合的方法，研究含有L酸和B酸中心具有异构化和脱水功能的Al催化剂、及含有B酸和L碱中心具有脱水和氧化功能的含V、Mo、或W的杂多酸和分子筛等催化剂作用下，葡萄糖转化为呋喃类化合物的反应机理；尝试耦合L酸、B酸和L碱等中心、设计将异构化、脱水和氧化多功能为一体化的含Al杂多酸及分子筛催化剂，研究其催化反应机理。确定关键中间体和关键反应步骤。明确易于水解的Al催化剂、易于溶解的含Al杂多酸、不易溶解的含Al杂多酸盐、以及便于分离和具有较大比表面积的含Al分子筛中活性中心的特性及其协同作用的机理，深化对其催化作用本质的认识，为设计制备由葡萄糖高选择性合成呋喃类化合物的催化剂提供理论支撑。对有效合理地利用生物质资源具有重要的意义。

葡萄糖是自然界中既廉价又丰富的单糖，其催化转化得到的呋喃类化合物是连接生物质化学和石油化工的很重要的平台化合物。以此为背景，采用高精度的量子化学和分子力场相结合的方法，研究了葡萄糖转化为呋喃类化合物的催化反应机理。研究成果如下：(1). 获得了溶剂环境对含有Al、Cu、Pd、V和W等单核金属催化活性组分的结构、及其与抗衡离子和溶剂分子等协同作用，从而影响催化性能的规律性认识；(2). 获得了杂多酸（H3PMo12O40和H3PW12O40）在溶剂环境中存在的稳定催化物种的结构、及其经由溶剂解产生的杂多酸阴离子、抗衡阳离子、以及分子等协同作用，从而影响催化性能的规律性认识；(3). 构筑了掺杂金属（Mo、V、Nb、Ta）的多功能MCM-41分子筛、以及用–RSO3H和–RNH2官能团修饰的多功能SBA-15分子筛的催化剂模型，并获得了催化活性中心的官能团的结构组成与催化性能的关系。同时，根据糖转化利用的研究现状，获得了Zr-SBA-15分子筛催化木糖转化为乳酸甲酯的反应机理；获得了在溶液中NaCl、B-酸及其抗衡离子促进或催化纤维二糖转化的分子作用机制。根据生物质转化利用的研究现状，初步探索了在Ni基催化剂模型上棕榈酸加氢脱氧的反应机理。该研究成果为理性设计碳水化合物的高效利用的催化体系提供了理论支撑。对有效合理地利用生物质资源具有重要的意义。在该项目的资助下，已经发表SCI收录论文12篇，发表中文核心期刊2篇，均为第一标注。已经培养毕业博士研究生2名，毕业博士研究生7名；正在培养在读博士研究生3名，在读硕士研究生4名。

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