类沸石骨架过渡金属硫属化物的设计合成及性质研究

项目名称： 类沸石骨架过渡金属硫属化物的设计合成及性质研究

项目编号： No.21301009

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 张仁春

作者单位： 安阳师范学院

项目金额： 25万元

中文摘要： 利用超四面体硫属原子簇取代沸石骨架中TO4是构筑开放骨架大孔硫属化物的有效途径。但是由于桥连硫属离子或有机硫醇的张角很小且呈现一定的刚性，骨架类型非常有限，而且很容易形成穿插降低骨架的孔隙度，进而限制了其应用前景。因此，抑制骨架穿插，并设计合成新型开放骨架硫属化物已成为开发多功能孔材料迫切需要解决的问题。本项目拟以表面可修饰的过渡金属硫属超四面体原子簇为结构单元，以角度为145 的咪唑类阴离子作为桥连配体设计合成类沸石型骨架。利用硫酚及咪唑衍生物不同取代基团的空间效应抑制穿插结构的形成，探索其对骨架拓扑结构以及孔道性质的影响规律，通过调节原子簇结构单元的尺寸、组成实现对这类材料的结构、性质(如吸附、半导体和光催化性质)的调变，为新型非穿插的多功能微孔材料的设计合成提供新的思路。

中文关键词： 沸石；咪唑；超四面体；硫属化物；原子簇

英文摘要： Replacing each TO4 in zeolite framework by a super-tetrahedral chalcongenide clusters has been proved an effective method to construct open-framework chalcongenides with large pores. However, due to the small and rigid angles of the bridging chalcogenide or thiolate anions, the variety of the frameworks is very limited, and the frameworks favor interpenetrating topology, which dramatically decreases the porosity and handers their potential applications. Therefore, it is urgent to prevent the formation of interpenetrating networks with the purpose to access novel multifunctional framework chacogenides with large pores. In this project, a new strategy was proposed to construct zeolitic framework transition-metal chalcogenides involving using surface-modifiable tetrahedral transition-metal chalcogenides clusters as SBUs and imidazolate anion with specific bridging angle of 145 as linker. We plan to ultilize the steric effect of substituent group on thiophenol and adazole derivatives to restrain framework interpenetration, probe their impacting on framework topology and channel characteristic, and modulate the structures and properties(adsorption, semicondctivity and photocatalysis) of the materials by tuning the size and content of the large tetrahedral building units, which may provide new ideas for the design sy

英文关键词： zeolite；Imidazole；super tetrahedron；chalcogenides；cluster