新型异质连接共价有机框架的设计、构筑与性能研究

Recently, covalent organic frameworks （COFs） has been one of the hottest topics in chemistry and material fields due to their outstanding properties and vast potential application prospect. To construct COFs with highly ordered structures and crystalline patterns, the reversibility of organic reactions is an unavoidable requirement during the synthesis, however, so far, only several organic condensation or polymerization reactions have been successfully employed to construct COFs. Thus, the development of new judicious strategy and the exploration of synthetic methodology are crucial and emergent tasks for advancing the research progress of this new class of porous materials. The construction of heterogeneously bonded covalent organic frameworks with highly chemical and water stability is a good option for us to tackle this dilemma. Through design and synthesis of novel heterogeneously bonded covalent organic frameworks that exhibit strong resistance to chemical and water media, this project here will focus in exploring new synthetic method for construction of these materials, which can provide the crucial basis for establishing systematic synthetic methodology of covalent organic frameworks. Furthermore, our work will firstly carry out the catalytic performance of these materials photo-degrading organic dyes molecules, which can fill the research gaps of covalent organic frameworks in this filed. Our research will also reveal how the inherent micro-structural characteristics for these frameworks dominate the photo-catalytic performance, and establish the relationship between their structures and properties, which can provide experimental and theoretical basis for design and construction of optimized functional materials.

近年来，共价有机框架由于其表现出的优异性能和广阔的应用前景而成为化学和材料科学领域的研究热点。要构筑具有高度结构有序和高结晶性的共价有机框架材料往往需要涉及可逆的有机反应，但目前能成功构筑出这类材料还仅仅局限于少数几个有机缩合或聚合反应。为了推动这类新型多孔材料进一步向前发展，必须找到新的策略和探索新的合法方法，而这是一项极具挑战性且紧迫性的课题。构筑较高化学和水稳定性的异质连接共价有机框架是解决此难题的一种有效方法。本项目拟通过设计和构筑具有较高化学和水稳定性的新型异质连接共价有机框架，探索构筑这类材料的新的合成方法，为建立系统的共价有机框架合成方法学提供重要依据；率先开展这类材料作为光催化剂在降解有机污染物方面的研究，填补共价有机框架在此领域的研究空白。通过揭示材料内在微结构特征如何影响其光催化性能，构建材料的结构与性能关系，为优化功能材料的设计与制备提供实验和理论依据。

共价有机框架由于其表现出的优异性能和广阔的应用前而激发在化学和材料领域科学家的极大兴趣。为了能推动共价有机框架材料进一步向前发展，必须找到新的策略和探索新的合法方法，而这是一项极具挑战性且紧迫性的课题。在共价有机框架的合成方法学方面，我们率先提出通过连接体交换和连接键交换法，实现了将无定型非孔的共价有机高分子（COP）转化成高结晶性多孔的，开辟出COF合成新的途径。在新型共价有机框架材料的设计合成与性能方面，我们设计合成了多个系列的新型共价有机框架材料，在碘蒸气吸附、去除污染物和Hg离子等领域表现出优异性能，展现出广阔的应用前景。新型共价有机框架复合材料方面，我们设计合成出具有特殊结构的共价有机框架复合材料，在烯烃的氢化催化中表现出优异的尺寸选择性和形状选择性，对重大挑战性的尺寸选择性催化材料的设计合成具有重要意义。