新型有序大孔材料的合成、结构及应用

Ordered macroporous materials with the pore size comparable to optical wavelengths have attracted great attention because of their unique optical properties and potential applications such as photonic bandgaps and optical stop-bands. Basic research into and production of new macroporous solids necessitates the preparation of new materials of particular structures, compositions and with new properties. This raises the bar in terms of the structural characterisation and extends a real challenge to the scientific community to fully understand the properties and potential applications of such materials. .In this proposal, we will study the synthesis, structures and the applications of ordered macroporous solids based on our previous research results, including (i) Synthesis of ordered macroporous materials. Design and synthesis new amphiphilic block copolymers as the template and construct macroporous materials with various structures, compositions and properties by the self-assembly of amphiphilic 
block copolymer and the inorganic source through microphase separation. Specially, synthesis different minimal surface-type structures through the multilayer core-shell microphase separation method. (ii) The structural and morphological study of the macroporous materials by electron crystallography. The structure of these materials is the key to their performance and the macroporous system can be considered as a good model system for crystallographic research, various structures, including structural relationship, epitaxial intergrowth and defect, will be studied thoroughly. (iii) Applications of the macroporous materials as the photonic crystal and in other fields. Different types of macroporous structures and compositions, especially the shifted minimal surface-type structures will be tested and studied experimentally and theoretically. .This project could provide significant opportunities in various research areas and open new horizons in porous materials, crystallography, nanotechnology and material science.

有序大孔材料由于孔道尺寸在光波长范围，具有独特的光学特性如光子带隙、光阻带等而备受关注。合成具有不同结构、组成及功能的新型大孔材料，对其进行深入的结构解析并探究其性能表现具有极其重要的理论和应用价值。本课题拟在前期研究基础上，(1)设计多种嵌段共聚物为模板，通过改变模板分子的结构及反应条件，使用微相分离与无机物种协同自组装合成具有不同结构、组成和功能的有序大孔材料，特别是通过多层核壳微相分离合成极小曲面大孔结构；(2)通过电子晶体学对所得大孔材料的结构，特别是缺陷及共生等进行解析，揭示不同类型模板分子导向形成孔道结构的机制，形貌与结构的形成机理，材料结构和功能之间的关系；(3)结合实验与理论探索具有不同结构及组成的大孔材料，特别是错位极小曲面结构在光子晶体及其它领域的应用。本项研究对于纳米科学、结构化学、晶体学和材料科学具有重要理论研究价值，并将为新型多孔材料的合成和应用打下良好的基础。

有序大孔材料由于孔道尺寸在光波长范围，具有独特的光学特性如光子带隙、光阻带等而备受关注。合成具有不同结构、组成及功能的新型大孔材料，对其进行深入的结构解析并探究其性能表现具有极其重要的理论和应用价值。本项目针对大孔及多级孔结构材料，在合成方法、晶体结构、形成机理、光学性能等重要科学问题开展了系统性的研究工作，取得了一系列创新性研究成果：.（1）发展了仿生合成双曲面大孔结构的方法，构筑并解析了多种复杂马鞍形双曲面结构，包括错位嵌套双primitive曲面以及热力学不稳定的单套gyroid常平均曲率曲面结构；发现了多种曲面的外延生长关系，提出了曲面转变过程的中间相态及菱形转变机理；通过108种嵌段共聚物作为模板导向无机材料合成的相图，发现了反胶束排列下有机/无机界面曲率的结构变化规律，揭示了一系列嵌段共聚物分子的组装原理。.（2）提出通过双套曲面骨架错位获得低对称全带隙光子晶体结构的思路，发现具有双套diamond曲面结构的锐钛矿型二氧化钛材料可以通过两套结构的相对位移，使其对称性从初始立方结构进行降低而出现全光子带隙，且带隙宽度及对组成成分介电常数的优化达到了蝴蝶翅膀中单套gyroid曲面的特性；通过使用两亲性嵌段高聚物模板和缩聚可控的钛源制备了全带隙二氧化钛三维光子晶体结构。.（3）实现了有序二维介孔沸石分子筛的突破，通过多功能模板剂导向法，在疏水端中引入偶氮基团，利用偶氮基团间的强π-π相互作用组装形成棒状胶束，通过亲水端的季铵盐导向作用匹配分子筛晶体结构的几何构型合成MFI型沸石骨架，得到了具有有序二维正方介孔结构的MFI型沸石，提出了双功能模板分子与分子筛晶体间匹配结构导向单元的设计概念。.项目执行期间，共发表标注本项目资助的SCI论文26篇，其中以通信作者发表文章22篇，授权发明专利1项，在国内外学术会议上做主题及邀请报告6次，培养学生中已毕业博士生2人。