含孤对电子杂原子的亚稳金属氧簇合物的聚合机理、可控合成及材料功能化

Polyoxometalates (POMs) have being received much attention and become a multidisciplinary research hot spot owing to a diverse compositional range and an enormous structural variety resulting in potential applications in catalysis, materials science，and so on. This project is based on the transition-metal cluster substituted polyoxotungstates and polyoxomolybdates with important active physical and chemical properties, which are constructed by metastable lacunary building blocks containing lone-pair electron heteroatom. By using high-resolution mass spectrometry along with x-ray single crystal analysis and quantum chemistry calculation, we will explore to determine the structures and composition of intact polyanions and fragments in solution to bridge the gap between solid-state and solution studies so that the key features of the self-assembly mechanisms of polyoxometalate clusters could be revealed. The results will be used to effectively synthesize the desirable structral and functional novel POMs containing lone-pair electron heteroatom by controlling the fragment assembly in solution. Furthermore, by using the prepared POMs, we will fabricate multifunctional molecular materials which are stable in solution for practical applications in electrochemical catalysis and heterogeneous catalytic oxidation. This study will make important progress in the study of POMs containing the subvalent main group atoms both theory and practice.

过渡金属氧簇合物（POMs）由于其结构和组成的多样性以及在催化、材料科学等领域的重要应用，成为多个学科的研究热点之一。本项目立足该领域中具有重要物理和化学性质的由含孤对电子杂原子缺位亚稳单元所形成的过渡金属及稀土离子取代的杂多钼酸和钨酸盐体系，采用高分辨质谱等技术测定其溶液体系中存在的完整离子及碎片种类，将溶液中碎片的结构信息与单晶结构测定所含有的建筑单元及量子化学计算结果进行比对，在理论上和实验上相互验证，架起固态结构与溶液结构间的桥梁，揭示反应体系中目标化合物的形成规律及成簇机理,从而指导具有特定结构并赋予其特殊性质的目标POMs的设计合成或可控合成。在此基础上，研制该类亚稳POMs在水溶液中能稳定存在的负载型功能材料和功能化方法，对其非均相催化和电化学催化性能进行研究。力求从根本和基础上在其聚合机理、可控合成及功能材料化这些多酸化学发展中长期存在的关键性挑战问题上取得重要进展。

过渡金属氧簇合物（POMs）由于其结构和组成的多样性以及在催化、材料科学等领域的重要应用，成为多个学科的研究热点之一。本项目立足该领域中具有重要物理和化学性质的由含孤对电子杂原子缺位亚稳单元所形成的过渡金属及稀土离子取代的杂多钼酸和钨酸盐体系，采用高分辨质谱等技术测定其溶液体系中存在的完整离子及碎片种类，将溶液中碎片的结构信息与单晶结构测定所含有的建筑单元及量子化学计算结果进行比对，在理论上和实验上相互验证，架起固态结构与溶液结构间的桥梁，揭示反应体系中目标化合物的形成规律及成簇机理,从而指导具有特定结构并赋予其特殊性质的目标POMs的设计合成或可控合成。在此基础上，研制该类亚稳POMs在水溶液中能稳定存在的负载型功能材料和功能化方法，对其非均相催化和电化学催化性能进行研究。力求从根本和基础上在其聚合机理、可控合成及功能材料化这些多酸化学发展中长期存在的关键性挑战问题上取得重要进展。