功能分子金属有机框架在二氧化碳氢化还原中的应用研究

项目名称： 功能分子金属有机框架在二氧化碳氢化还原中的应用研究

项目编号： No.21471126

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： 林文斌

作者单位： 厦门大学

项目金额： 85万元

中文摘要： 二氧化碳氢化因可将二氧化碳转变成化工生产的基础原料而备受关注。相比于非均相金属/氧化物等工业二氧化碳氢化催化剂，过渡金属配合物小分子催化剂具有催化效率高，反应机理清晰等优点，但这类均相催化剂主要在溶液中使用，其实际应用被氢气在溶液中的溶解度和反应所需的较高压力所限制。本报告详细阐述了将过渡金属小分子催化剂固化到多孔结构中，进行固-气界面相二氧化碳氢化反应的方法。我们将用金属有机框架化合物组装的成熟技术将小分子催化剂转变成多孔固体催化材料，使这些固体小分子催化剂不再受氢气在溶液相中溶解度的限制。同时，固定在多孔结构中的催化剂分子在空间上的相互分离，也可使其稳定性得到提高。我们还将系统探索这些小分子催化剂在固-气界面的催化效率、选择性和催化机理，并且寻找溶液相中不能稳定存在的全新固体小分子催化剂。该项研究不仅能为二氧化碳氢化和小分子催化研究提供全新的视角，并且将在工业上具有潜在价值。

中文关键词： 功能分子材料；金属有机框架；多孔材料；二氧化碳催化氢化；非均相催化

英文摘要： Hydrogenation of carbon dioxide to primary chemical feedstock has attracted a lot of attention from both academia and industry. The hydrogenation of carbon dioxide can be catalyzed by heterogeneous catalysts such as transition metal or metal oxides. Transition metal complexes can also serve as highly efficient catalysts with well-defined catalytic cycles. However, industrial application of such homogeneous hydrogenation catalysis is limited by the solubility of hydrogen in solution, which leads to required high pressure of hydrogen in the process. Here we propose to immobilize those molecular catalysts into porous solid structures, through the assembly strategy of metal-organic frameworks. The assembled porous molecular solids can serve as catalysts for hydrogenation of carbondioxide at the solid-gas interface. The solubility of hydrogen in solvent will no longer be a constraint on the catalytic rates. Moreover, site isolation of the embedded molecular catalysts will prevent bimolecular decomposition from happening, thus stabilizing the catalysts. We will carry out systematic studies on the catalytic activity, product selectivity and turn-over mechanism of these porous molecular solids. We also plan to search new molecular catalysts that are unstable under traditional homogeneous catalytic conditions but highly active on the solid-gas interface.This research project will not only broaden our knowledge of fundamental chemical transformation of carbondioxide and molecular catalysis, but also have its significance in industrial processes.

英文关键词： Funcional Molecular Materials;Metal-Organic-Frameworks;Porous Materials;CO2 Hydrogenation;Heterogeneous Catalysis