【作者】 李辉；

【导师】 方千荣；

【作者基本信息】 吉林大学 ， 无机化学， 2020， 博士

【摘要】 共价有机框架（COF）材料是一种新型的结晶性有机多孔聚合物。这种材料主要是由一些轻质元素（H,B,C,N和O等）组成的构筑单元通过可逆共价键连接而成的框架结构。COF一般具有高的比表面积、高的孔隙率、优良的稳定性和低的密度。因此在气体存储与分离、催化、光电和生物材料等领域具有广泛的应用,并且受到科学家们越来越多的关注。在过去的十几年,共价有机框（COF）架材料的报道主要集中于2D COF,而3D COF的设计合成发展缓慢,尤其是功能化的3D COF的设计合成一直是比较困难。这主要是因为3D COF的设计与合成比2D COF困难。首先,合成3D COF的构筑单元要具有刚性结构,尤其对于功能化的构筑单元很难形成高结晶性的3D COF。而且3D COF的框架结构容易发生穿插现象,化学稳定性较差,影响了其应用的广泛性。因此合理的设计合成功能化的3D COF对于丰富其结构多样性和拓展其应用是至关重要的。根据目前3D COF在功能化和应用上所存在的问题,本论文主要通过不同的策略设计合成了三类常见的功能化3D COF拓扑（ctn,dia,和pts）结构。并将三类功能化的3D COF应用于一锅法串联催化、CO₂的选择性分离和导电材料上。研究内容主要分为以下三个部分。（1）目前3D COF的设计合成主要是通过一种可逆键型在溶剂热条件下合成,而我们通过一种新策略首次合成了同时具有两种键型的3D COF（DL-COF）,所得到的3D COF具有高的比表面积,而且和其他3DCOF相比具有很好的气体储存能力。另外由于本工作中合成的DL-COF同时含有酸碱两种催化位点,在用于一锅串联催化反应中表现出优良的催化性能。这种新的合成策略不仅丰富了3D COF的构筑方法,而且拓展了功能化3D COF的应用。（2）共价有机框架（COF）材料,是一种结晶型的有机多孔聚合物。一般主要是通过溶剂热方法合成,这种方法一般能耗高而且不环保。我们第一次通过离子液体的方法合成了三种3D COF（3D-IL-COF）,而且部分离子液体负载在3D-COF的孔道中,这种方法在常温常压下短时间内即可得到高结晶性的3D COF。最主要的是在合成3D COF材料的同时,也得到了离子液体功能化的3D COF,其中离子液体功能化后的3D-IL-COF-1对CO₂具有很好的选择性分离效果,这种简单的合成功能化3D COF的方法为其进一步的应用奠定了基础。（3）功能化的3D COF的设计合成对于拓展其应用的多样性非常重要,而目前很少有关于导电性的3D COF的报道,因此我们将具有电学性质的TTF衍生醛基物作为构筑单元,成功合成了两种具有pts拓扑的TTF-3D-COF（JUC-518和JUC-519）。特别是JUC-518 COF是非穿插的pts拓扑结构,比其他穿插的pts拓扑的3D COF拥有更高的比表面积(>3000 m²g^-1)。随后将TTF-3D-COF经过I₂掺杂后形成了含有离子自由基的电子转移复合物,并且在I₂掺杂后的两种TTF-3D-COF都表现出良好的半导体材料特性。更多还原

【Abstract】 Covalent organic frameworks（COF）,as an exciting new type of crystallineporous polymers,are made from lightelements,typically H,B,C,N,and O,which crystallize into periodic networks by the formation of reversible covalent bonds.Owing to their high porosity,large specific surfacearea,and good thermal/chemical stability,the COF materials have attracted much attention for considerable potential in gas storage and separation,catalysis,organic electronics,and many others.Over the past decade,most of the reported work on COF,however,were focused on 2D COF with layered eclipsed structures.Especially functionalized 3D COF,have recently attracted extensive interest due to their unique porous features and excellent performances.Owing to the design and synthesis of 3D COF are more difficult than those of 2D COF.Firstly,the crystallization problems are more significant for 3D COF and the synthesis conditions are more rigid and precise for 3D frameworks,especially for those monomers with functional moieties.Besides,the phenomenon of interpenetration is universal in 3D COF’structures and the chemical stabilities of 3D COF are generally weak,resulting in the limited applications of 3D COF.Therefore,designing 3D functionalized COF is very important for expanding their structural types amd applications.Based on the questions mentioned above,We used different strategies to prepare a series of functionalized 3D COF with three different topos（dia,ctn,pts）.And their performances in one-pot cascade catalysis,the seperation of CO₂ and electrochemistry were discussed in this thesis.This thesis includes the following three parts:（1）Covalent organic frameworks（COF）are anemerging class of porous crystalline polymers with broad potential applications.So far,the availability of 3D COF is limited and more importantly only one type of covalent bond has been successful used for 3D COF materials.Here,we report a new synthetic strategy based on dual linkages that leads to 3D COF.The obtained 3D COF show high specific surface areas and large gas uptake capacities,which makes them the top COF material for gasuptake.Furthermore,we demonstrate that the new 3D COF comprise both acidic and basic sites,and act as excellent bifunctional catalysts for one-pot cascade reactions.The new synthetic strategy provides not only a general and versatile approach to synthesize 3D COF with sophisticated structures but also expands the potential applications of this promising classof porous materials.（2）Covalent organic frameworks（COF）are an emerging class of porous crystalline polymers with widerange of potential applications.However,the availability of 3D COF is still limited,and their synthesis is confined to the high-temperature solvothermal method.Here,we report for the first time a general andsimple strategy to produce a series of 3D ionic liquid（IL）-containing COF（3D-IL-COF）by using IL as a greensolvent.The syntheses are carried out at ambient temperature and pressure accompanied by a high reaction speed（e.g.,only three mins for 3D-IL-COF-1）,and the ILcan be reused without activity loss.Furthermore,the 3DIL-COFs show impressive performance in the separation of CO₂/N₂ and CO₂/CH₄.This research thus presents a potential pathway to green large-scale industrial production of COF（3）The functionalization of three-dimensional covalent organic frameworks（COF）is essential to broaden their applications.However,the introduction oforganic groups with electroactive abilities into 3D COF is still very limited.Herein we report the first case of tetrathiafulvalene-based 3D COF（3D-TTF-COF）withnon-or 2-fold interpenetrated pts topology and tunableelectrochemical activity.The obtained COF show highcrystallinity,permanent porosity,and large specific surfacearea(up to 3000m²g^-1).Furthermore,these TTF-based COF are redox active to form organic salts that exhibit tunable electric conductivity(as high as 1.4×10^-22 S cm^-1at 120°C)by iodine doping.These results open a way toward designing electroactive 3D COF materials and promote their applications in molecular electronics andenergy storage.更多还原