分子筛催化葡萄糖异构化反应的理论研究

项目名称： 分子筛催化葡萄糖异构化反应的理论研究

项目编号： No.21473137

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 杨刚

作者单位： 西南大学

项目金额： 80万元

中文摘要： 发展生物质能是缓解乃至解决能源危机的重要途径。葡萄糖异构化生成果糖是生物质转化最为关键的反应之一。本项目拟运用密度泛函等理论方法，深入研究分子筛催化葡萄糖异构化反应的若干关键性问题。首先研究没有溶剂时分子筛催化葡萄糖异构化生成甘露糖的反应机理并与生成果糖的结果进行比较；然后依次研究溶剂参与葡萄糖异构化反应的机制并阐明其对反应途径和产物分布的影响、不同锡活性物种（骨架和担载）如何影响异构化反应途径和产物分布及担载的锡物种尺寸与反应活性之间的关系、不同骨架金属离子催化异构化反应机理并阐明金属锡对异构化反应的独特催化效果、分子筛孔道效应在异构化反应中所起的重要作用等内容。从而深入而全面的理解葡萄糖异构化反应的相关机理及各因素对该反应途径和产物分布的影响，为葡萄糖（最丰富的单糖）和纤维素生物质的催化转化和有效利用提供重要的研究思路，也为多相催化剂的优化和设计提供重要的科学依据。

中文关键词： 分子筛；异构化反应；密度泛函；催化；生物质

英文摘要： The development of biomass energy is an important route to alleviate and even settle the energy crisis that we are facing. The isomerization of glucose to form fructose has been listed as one of the key reactions for biomass conversions. In this project, density functional and other theoretical methods are used with the aim to have an in-depth study on the related issues of glucose isomerization reaction. First we study the reaction mechanism of glucose isomerization to mannose in absence of solvents,and the results are compared with those of fructose. Then we successively study the mechanisms of how solvent molecules participate in the isomerization reaction and affect the reaction routes and product distribution, the reaction routes and product distribution for different tin active species (framework and supported) and the correlation between the size of extra-framework tin species and the catalytic effects, the reaction mechanisms of different substituted metal ions with aim to clarify the unique catalytic effects of the tin species as well as the effects of zeolite channels played during the isomerization reaction. In this way, an in-depth and comprehensive understanding will be achieved for the mechanistic aspects of glucose isomerization reaction and the various influencing factors on the reaction routes and product distribution. Significant research clues are thus provided for the catalytic conversions and effective utilization of glucose (the most abundant monosaccaride) and cellulosic biomass; meanwhile, scientific advice is given as to the optimization and design of heterogeneous catalysts.

英文关键词： zeolite;isomerization reaction;density functional;catalysis;biomass