基于刚性羧酸配体的金属-有机凝胶的结构调控与催化应用研究

Metal-organic gels (MOGs) have attracted growing interest as novel soft materials for adsorption, sensing, luminescence, catalysis and others due to the incorporation of coordination interactions and potential application in many areas. MOGs are related to coordination polymers, which have been a hot topic during last two decades. Comparing with highly ordered aggregation of crystalline metal-organic frameworks and random aggregation of amorphous coordination polymers, aggregation process intermediate of MOGs receives much less attention. Due to incorporation of metals, MOGs may have some interesting functionalities as novel materials for adsorption, sensing, luminescence, catalysis and others. However, it is not often possible to predict whether a MOG phase will form resulting from the fact that gels are based on a liquid and a gelator. Gels are potentially complex due to complication of supramolecular interactions, and the interaction between two components is also little to be understood. To date, ‘rules’ based on organogelators have provided the main rational approach to generate metallogels with a desired function. We are interested in new strategies to coordination-directed gels. To generate a gel with a desired function, it is important that the constituent molecular blocks (gelator) be designed so as to contain the required structural features. In this project, a group of MOGs are rationally designed on the basis of rigid carboxylates. The relationship between the structure and the property of MOGs will be investigated. A novel group of catalytically active MOGs incorporating homogeneous catalysts are designed. This project aims to exploit a group of novel functional organic-inorganic hybrid gel materials with unique luminescent, sorption and catalytic properties.

金属-有机凝胶作为一种新型软物质材料，是由金属离子和有机配体在特定的溶剂中形成的，在多个领域具有潜在应用价值。基于刚性有机羧酸配体的金属-有机凝胶经过超临界干燥后具有独特的多级孔道结构，并且具有较大的比表面积。和同类材料相比，金属-有机气凝胶材料可通过简单易得的原料制备，具有制备方法简单、成本低、可较大规模生产等优势。然而对于这样一类具有极大发展潜力的材料，目前国内外尙缺乏系统研究。本项目将对此类金属-有机凝胶的形成机理进行探讨，并系统研究金属-有机凝胶结构和催化性能之间的关系。通过调控金属-有机凝胶的微观结构，从而优化其吸附、发光、催化等性能，并重点开发一类高效均相催化剂负载体系。本项目的成功实施将发展一类具有较大孔洞的高比表面积有机-无机杂化凝胶功能材料，具有重要的催化应用前景。

金属-有机凝胶作为一种新型软物质材料，是由金属离子和有机配体在特定的溶剂中形成的，在多个领域具有潜在应用价值。本项目通过系统研究发现刚性桥连羧酸有机配体与金属离子反应通过配位键驱动可有效地形成金属-有机凝胶，基于刚性有机羧酸配体的金属-有机凝胶经过干燥后具有独特的多级孔道结构，并且具有较大的比表面积。和同类材料相比，金属-有机气凝胶材料可通过简单易得的原料制备，具有制备方法简单、成本低、可较大规模生产等优势。对此类金属-有机凝胶的形成机理进行探讨，并系统研究了金属-有机凝胶结构和催化性能之间的关系。通过调控金属-有机凝胶的微观分子结构，从而优化其吸附、发光、催化等性能。首次合成了结合气凝胶和金属-有机框架优点的具有层次孔的金属-有机气凝胶材料；得到了具有多重不同寻常刺激响应性质的金属-有机凝胶体系；并发展了可用于化学固定CO2的多相凝胶催化剂。在金属-有机凝胶研究基础上发展了一类新的动态共价凝胶，将动态共价凝胶与微流体技术结合成功实现手性负载催化；并把超分子笼状化合物作为结构基元引入超分子凝胶。通过本项目的研究，澄清了配位键导向的金属-有机凝胶形成的机理，理清了影响金属-有机凝胶形成的各种因素，发展了一类具有层次孔的高比表面积凝胶功能材料，为进一步实现可控的层次自组装提供了基础，并具有重要的应用前景。