酮选择性氧化多级孔金属氧化物复合及负载催化材料合成及其传质-氧化性能调控

项目名称： 酮选择性氧化多级孔金属氧化物复合及负载催化材料合成及其传质-氧化性能调控

项目编号： No.51472179

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 一般工业技术

项目作者： 郑春明

作者单位： 天津工业大学

项目金额： 83万元

中文摘要： 在酮和环酮类分子转化为酯和内酯的非均相Baeyer-Villiger(BV)催化氧化过程中，催化材料催化效率低和重复使用稳定性差仍是亟待解决的关键科学问题。本课题基于增强酮类分子向催化材料表面的传质-氧化能效，利用软、硬模板法设计并控制合成多级孔复合及负载金属氧化物非均相BV催化材料。充分利用其微、介、大的多套孔结构配合、比表面积大的结构优势和易于实现材料表面多种不同价态组分复合的制备特性，形成与不同类型酮类分子的传质动力学匹配，达到适应不同反应物酮类和生成物脂类分子的孔结构和表面活性位化学环境精细调控。深入研究传质吸附与氧化性能高效结合的内在机理。通过本研究将掌握多级孔复合及负载金属氧化物BV催化材料的制备、催化及反应机制，揭示材料结构形貌-物理化学属性-催化性能之间的内在关联，从而为高性能BV催化材料的设计提供理论依据和方法支持。

中文关键词： 金属氧化物；催化材料；多级孔；Baeyer-Villiger；氧化

英文摘要： During the heterogeneous Baeyer-Villiger (BV) catalytic oxidation process from ketones and cyclic ketones to esters and lactones, how to improve the catalytic efficiency and reuse stability are the key scientific problems to be solved. Based on the mass transfer-oxidation enhancing effect of the ketones and cyclic ketones to the surface of the catalytic materials, we will systematically prepare the hierarchical porous mixed and loaded metal oxides as the heterogeneous BV catalytic materials using the soft- and hard-template methods. Taking full advantage of the micro-, meso-, and macroporous distributions of hierarchical pores, high specific surface area and easy nano-scale composites of multiple mixed valence consitituents, the dynamic of mass tranfer of the ketones will be effectively matched and the number of the catalytic active sites will be greatly increased. Pore structrue and surface chemistry of active sites of the hierarchical catalyst will be finely adapted by reaction characteristics of ketone and lipid molecules.After that, the internal and conjoint mechanism of diffusion and oxidative mechanism will be researched in depth. The successful synthesis of heterogeneous BV catalytic materials with high catalytic efficiency and good reuse stability will be our objective by effective design, preparation, catalysis and mechanism research. This project is expected to effectively improve the diffusion and absorption capacity of the catalysts surface and the rate of the chemical reaction for the heterogeneous BV catalytic materials. The inherent relationship between the material structures and morphology, the surface physical and chemical properties and the catalytic properties will be mastered. Hence, in this project, the theoretical basis and method support for the design of hetereogeneous BV catalytic materials with high catalytic properties will be provided.

英文关键词： metal oxides;catalytic materials;hierarchical pores;Baeyer-Villiger oxidation