镓氧化物载金纳米体系催化的醇液相选择氧化研究

项目名称： 镓氧化物载金纳米体系催化的醇液相选择氧化研究

项目编号： No.20873026

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 化学工业

项目作者： 曹勇

作者单位： 复旦大学

项目金额： 35万元

中文摘要： 针对纳米金催化液相选择氧化等精细有机催化过程所存在的问题，本项目研究了负载型纳米金催化剂结构和其催化性能之间的认知。在醇液相分子氧选择氧化反应中，研究了一系列具有不同组成、晶相及表面特性的镓基氧化物载金纳米催化剂，发现特定组成的镓-铝复合氧化物固溶体中镓-铝组分间的协同效应可促进纳米Au对醇的催化活化。在对醇、胺等多组分原料共存的复杂反应体系的选择氧化及定向催化转化研究中，成功地将对以镓基氧化物为主的催化载体的筛选范围扩大到同时具有酸/碱活性位等特性的羟基磷灰石等天然矿物载体中，发现羟基磷灰石担载纳米Au可剂具有独特的"多功能性"，具体表现为其可同时催化选择氧化-脱水缩合等多步反应，实现醇、胺或羟胺等多组分原料高效"一步"选择氧化制取亚胺、肟等重要中间体。在此基础上，广泛研究了镓氧化物、羟基磷灰石、氧化钛、氧化铈等多种材料为载体的负载型纳米Au催化材料的催化氧化/还原性能。在硝基还原反应中，发现氧化钛负载纳米Au可在常温常压下催化CO/H2O选择还原硝基化合物。这些认识有助于指导发展用于液相绿色的精细有机合成的新一代高活性高选择性纳米金催化剂及相关催化体系。

中文关键词： 多相催化；醇；液相氧化；纳米金；氧化镓

英文摘要： Supported gold nanoparticles have recently emerged as excellent catalysts for a broad range of organic transformations under mild conditions. To address the key aspects associated with the supported gold catalysts applicable for selective transformation of organic compounds in the liquid pahse, we focus our study on a novel solid catalyst system formed by gold deposited on a wide range of supports including nanocrystalline gallium oxides or Ga-containing mixed oxides, titania, ceria and hydroxyapatite etc., aiming to gain a fundamental understanding of the catalytic properties of the gold catalysts for green and sustainable chemcial synthesis under molecular level. The reason for this choice is that gallium oxide has emerged as an exceptional catalytic or supporting material highly efficient for a wide range of redox reactions, and it is also known that significantly modified surface properties could be achieved on Ga-containing mixed oxides. Special attention has been paid to the investigation of the influence of the nature of the gallium oxide supported, Au particle size, the preparation method, particularly the specific structure of the Au-oxide interface, on the catalytic activity of the gold nanocatalysts for liquid phase aerobic alcohol oxidation. Having established the key structural features required for high performace alcohol oxidation, several other environmentally benign and industrially attractive Au-based catalytic protocols have also been sucessfully developed including the tandem synthesis of imine compounds as well as selective reduction of nitro compounds by taking full advantagesd of the unique multifunctional nature of the supported gold catalyst system. We believe that the reaction chemistry established in this project can open new routes to selective functional transformations in organic synthesis and have important implications in the fundamental understanding of the catalytic origin of Au nanoparticles.

英文关键词： heterogeneous catalysis; alcohol; liquid oxidation; nanogold; gallium oxide