多酸活性单元-稀土配合物复合材料探索

There have been rapidly developed the POMs based materials during the recent years, many farmous scientists have reported tremendous interesting results in the top ranked journals. Among the investigations on the properties and their potential applications of the POMs, the catalytic properties have mostly been studied. Some shortages of the POMs, eg. smaller surface areas, higher water solubility and lower thermal stability, still have not been totally solved, which has been the major obstruction for the development of the field. How to improve the water solubility and thermal stability have been the key to the most difficulty of the study on the catalytic properties. Moreever, due to the special structural and property characteristics, the active sites are easily dispersed into the whole POM molecule, which reduce the catalytic activity in certain degree. How to capture and stablize the active POM sub-units will also the key to improve the catalytic ability. This project, aiming at the most recent reported results and combining our research backgrounds and results, raises an idea to capture and stablize the active POM sub-units by coordinated lanthanides, and then to investigate them throughtly by structural design, property study and structure-property relationships and so on. It is expected to obtain some new composite materials based on POMs and lanthanides with excellent catalytic activities and utilites, and then to provide some useful information for the basic study and utility investigations on the materials of this field.

多酸及其相关材料近年来得到迅猛的发展，许多著名的科学家在顶尖专业刊物上发表了大量出色的研究结果。在多酸的性能与应用的研究中，其催化性能是研究得最多的，但多酸本身的一些缺陷，如比表面积相对较小、水溶性大和热稳定性不好等一直没得到根本的解决，大大阻碍了相关研究的进展，如何改变其水溶性和提高其热稳定性是基于多酸催化剂方面研究的难点和重点！另外，由于多酸特有的结构和性质，其活性位点易在整个多酸分子力分散，这在某种程度上降低了多酸的一些催化性能，如何捕获并固化多酸的有效催化活性单元也是提高其催化性能的关键！本项目基于国际上最新的研究发现，结合本人长期的研究基础，提出以稀土配合物来捕获并稳定最新发现的一些有催化活性的多酸基元的设想，通过结构设计、性能研究、构效关系等系统地研究所获得的复合物，以达到提高已有催化活性的多酸单元材料的综合性能和使役特性，为该类材料的基础研究乃至实际应用提供理论依据。

多酸因其独特的电子存储能力及丰富多样的结构特征，在催化领域有着重要的应用前景。然而其水溶性大，比表面积相对较小等本身自有的缺陷，大大阻碍了相关研究的进展。本项目通过有机功能配体的设计，利用稀土/过渡金属有机配合物来捕获并稳定具有催化活性的多酸单元，使其均匀地分散在框架材料内部，提高材料催化活性。并利用材料内部阴离子-π，氢键等弱的相互作用力，提高材料的热、化学稳定性。经过四年研究探索，合成了一系列具有特殊的光、电、磁性能的多酸基材料，并对材料在有机污染物降解，苯甲醇氧化，光催化分解水产氢，气体吸附存储等方面的应用展开详细研究，取得了一些有意义的成果。详细剖析了材料的结构特征、各组分单元对结构的调控作用及对性能的影响等，总结归纳了性能与结构之间的内在联系，为进一步拓宽多酸材料的研究打下了良好的基础。在本项目研究过程中，发表有该基金资助号的学术论文21篇，4项专利获得授权，培养了5名博士，1名硕士。