二维共价有机骨架材料的非破坏性插层剥离与应用

Two-dimensional ordered covalent organic frameworks (COFs) are considered to be layered materials that formed by the stacking of graphene-like two-dimensional polymers. Synthesis of single-layer or few-layer COFs is an important route to change the relevant physicochemical properties of COFs, to expand the scope of their applications, and to enhance their performance in many fields. However, the current research is still hampered by the effective preparation of abundant two-dimensional COFs. In order to overcome the problem of poor structural stability and chemical stability of layered COFs during the exfoliation process, a non-destructive intercalation and exfoliation route was proposed, and the mass production of two-dimensional single-layer or few-layer two-dimensional COFs will be achieved. The project will focus on the influence of the reaction conditions and parameters on the intercalation of a series of layered COFs, systematically reveal the rules of their structure change during intercalation, and determine the non-destructive and controllable intercalation conditions. The project will also investigate the efficient exfoliation of the resulting intercalation compounds, establish a new method for the preparation of single-layer or few-layer COFs, and systematically compare and explore the potential and advantage of the resulting two-dimensional COFs in the fields of catalysis and energy storage. The research results of the project are expected to promote the large-scale preparation and industrial application of two-dimensional COFs materials.

二维有序共价有机骨架材料(COFs)被认为是由类石墨烯单层二维高分子经过堆积形成的层状材料。合成单层或寡层二维COFs，是调变COFs相关物理化学性质，进一步拓展应用范围，提升相关性能表现的重要方法和手段。然而，目前相关研究工作仍受困于COFs的有效制备。本项目针对层状COFs材料在剥离过程中结构稳定性和化学稳定性差的难题，创新提出基于层状有序COFs材料的非破坏性插层剥离制备路线，以突破单层或寡层COFs二维纳米材料宏量制备的瓶颈问题。项目将重点研究一系列层状COFs材料在其插层过程中各反应条件和参数的影响，系统性揭示其插层过程中的结构变化规律，确定其非破坏性可控插层条件，研究所得插层化合物的高效剥离，建立起单层或寡层POFs二维纳米材料的制备新方法，并系统比较和探索所得二维COFs在催化及储能等方向的潜能和应用优势。项目研究成果有望促进二维COFs材料的规模化制备及产业化应用。

将层状共价有机框架（COFs）剥离为单层或寡层二维COFs纳米片，是调变COFs相关物理化学性质，拓展应用范围，提升相关性能表现的重要方法和手段。本项目针对层状COFs材料在剥离过程中结构稳定性和化学稳定性差的难题，开发基于层状有序COFs材料的非破坏性插层剥离制备路线，建立起单层或寡层COFs二维纳米材料的高效制备新方法，并系统比较和探索所得二维COFs在催化及储能等方向的潜能和应用优势。项目发现了基于酸-碱反应推动力的COFs可逆插层现象，开发了基于磷酸质子化的层状COFs非氧化插层剥离方法、基于硫酸/过硫酸铵体系的层状COFs可控氧化插层剥离方法、微波辅助的COFs硝基功能化修饰及高效剥离方法。在此基础上，探究了所得COFs纳米片在金属离子电池、光催化、电催化、基因传递、荧光探针等领域的应用前景，开展了边缘氧化、质子化COFs的光催化制H2研究，揭示了其性能提升机理；开展了COFs基单原子催化剂的活性位设计及其电催化CO2RR应用研究；制备了一系列COFs衍生的多级结构碳材料并在电催化ORR方面展现出良好的应用前景；概念性地证明了功能化COFs纳米片的在基因传递中的应用潜力。基于所得研究成果，发表SCI论文10篇，各项考核指标均超额完成。