Development of Highly Functionalized Hybrid Catalysts Aiming Toward Environmentally Friendly Processes for Materials Transformation

在这项研究项目中，我们展示了一种有效的绿色和可持续化学方法，通过设计以无机固体为大配体的多相金属催化剂，并发现它们对各种材料转化具有优异的催化性能，包括选择性氧化、碳-碳键形成反应、一锅合成、脱卤化和固定二氧化碳。基于羟基磷灰石、蒙脱石和水滑石作为先进载体的独特性质，各种针对目标反应的杂化催化剂被创造出来。包含多相金属催化剂的催化体系可以在实现简单和清洁的有机转化方面提供显著的好处，因为它们具有以下优点：(1)它们允许使用无污染的氧化剂；(2)它们具有高的催化活性和选择性；(3)它们具有很高的底物耐受性；(4)它们允许简单的加工过程和催化剂的容易回收，以及(5)它们可以回收。通过应用配位化学的概念，我们开发了一种制备纳米结构金属物种的方法，该方法比以往的固载金属催化剂的合成方法简单得多，并为制备组成和分布均匀的具有催化活性的化合物提供了强有力的方案。

In this research project, we demonstrated an effective approach to Green and Sustainable Chemistry by designing heterogeneous metal catalysts using inorganic solids as macroligands, and found their outstanding catalytic performances for a variety of material transformations including selective oxidations, carbon-carbon bond-forming reactions, one-pot syntheses, dehalogenation, and fixation of carbon dioxide. Based on the unique properties of hydroxyapatite, montmorillonite, and hydrotalcite as advanced supports, various hybrid catalysts were created with respect to the target reactions.Catalytic systems incorporating the heterogeneous metal catalysts can offer significant benefits in achieving simple and clean organic transformations because they have the following advantages : (i)they allow the use of non-polluting oxidants, (ii)they possess high catalytic activity and selectivity, (iii)they have high substrate tolerance, (iv)they allow a simple work-up procedure and easy recovery of the catalyst, and (v)they are recyclable. By applying concepts from coordination chemistry, we have developed a preparation for nanostructured metal species that is much simpler than previous synthetic methods for solid-supported metal catalysts and provides a strong protocol for preparing catalytically active compounds that are uniform in composition and distribution on solid surfaces.