CN107915658B - 基于金刚烷单元的三维共价有机框架材料及其合成和应用 - Google Patents
基于金刚烷单元的三维共价有机框架材料及其合成和应用 Download PDFInfo
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Abstract
本发明公开了一种基于金刚烷单元的三维共价有机框架材料的合成方法:在有机溶剂中,将四面体构型的四(4‑苯胺基)金刚烷和四(对苯醛基)芘均匀混合,然后加入催化剂醋酸水溶液,经过加热晶化、索氏提取洗涤和加热真空干燥,可得到三维共价有机框架材料COF‑DL602。本发明方法得到的COF‑DL602材料具有高的比表面积及规则有序的微孔结构,并在气体(如H2、CH4和CO2)吸附实验中,表现出了大容量的气体吸附能力和较高的CO2/N2气体选择性。因此,COF‑DL602可以作为一种优异的气体吸附材料,应用于气体存储及分离。
Description
技术领域
本发明属于共价有机框架材料(COFs)领域,具体涉及一种基于金刚烷单元的三维共价有机框架材料及其合成方法。
背景技术
共价有机框架材料(COFs)是一类新兴的由开放孔洞所构成的晶型有序的有机骨架结构材料。这类材料骨架中不含有金属元素,完全是由含有轻元素(H,C,N,B,O,Si等)的有机构筑单元通过强共价键连接而成的多孔材料。在材料结构上,COFs具有骨架密度较低、比表面积大、孔道规则有序、可控的物理化学性质、易功能化以及合成策略多样化等特点。因此,COFs材料在气体吸附/储存/分离、异相催化、荧光探针、光电器件、光解水制氢及质子传导等领域展示了非常大的应用潜力。在多孔材料评价体系中,一个重要衡量指标是材料的气体吸附能力。值得一提的是,由于COFs材料在结构上具有以上所提到的特点,这样COFs作为一类吸附材料在气体的存储及分离方面呈现出了其优异的性质。
根据广义的拓扑结构理论,COFs材料主要分为二维(2D)COFs和三维(3D)COFs材料两大类。到目前为止,大量文献报道了有关2D COFs材料的合成及其应用。然而,有关3DCOFs材料领域的研究却只有极少数的报道。与2D COFs材料的层状堆积结构所不同的是:在3D COFs材料中,分子构筑单元通过共价键连接组装形成一种特定的三维空间网络结构,这种3D结构具有更大的比表面积和更多的空间开放位点,因此3D COFs在气体吸附存储应用上也更具有潜力。
发明内容
本发明目的在于克服现有的三维共价有机框架材料在材料合成及其应用方面的难题,提供一种基于金刚烷单元的三维共价有机框架材料及其合成方法和应用。
为了实现上述目的,本发明提供了如下的技术方案:
一种基于金刚烷单元的三维共价有机框架材料的合成方法,包括如下步骤:
将四面体构型的四(4-苯胺基)金刚烷(TAPA)和四(对苯醛基)芘(TFPPy)加入到安瓿瓶中,加入有机溶剂,超声混合均匀,然后加入催化剂醋酸水溶液,将安瓿瓶置于液氮中进行冷冻,抽真空并火焰封管,经过加热晶化、索氏提取洗涤和加热真空干燥,即可得到三维共价有机框架材料COF-DL602。
进一步,所述的四(4-苯胺基)金刚烷和四(对苯醛基)芘的摩尔比为1:(0.5-1);最佳摩尔比为:1:1。
所述的有机溶剂为邻二氯苯、邻二氯苯/均三甲苯的混合溶剂、或邻二氯苯/1,4-二氧六环/N,N-二甲基乙酰胺的混合溶剂;最佳溶剂为:邻二氯苯。
进一步,所用的有机溶剂和醋酸水溶液的体积比为(6-10):1;最佳体积比为:10:1。
所用醋酸水溶液的浓度为3M-9M;最佳醋酸水溶液的浓度为:6M。
进一步,所述反应的温度为120-180℃,最佳反应温度为:140℃;反应时间为3-30天,最佳反应时间为:5天。
上述方法合成得到的三维共价有机框架材料可应用于多种气体的吸附、存储及选择性分离,具体用于吸附H2、CH4和CO2及选择性分离CO2/N2气体。
本发明具有如下优点:
1、本发明首次利用含有金刚烷的单元构筑了一种新型3D COF材料;在共价有机框架材料研究领域中,提供了一种新的COF合成方法;
2、通过本发明方法得到的COF-DL602材料具有高的比表面积、规则有序的孔道和均匀分布的微米孔径;
3、COF-DL602材料在气体H2、CH4及CO2吸附实验中,表现出了大容量的气体吸附能力和较高的CO2/N2气体选择性,极大地拓展了COF材料在气体吸附、存储、分离领域的应用。
附图说明
附图是结合本发明的实施例一起用于解释本发明,并不构成对本发明的限制。在附图中:
图1为本发明所合成COF-DL602和原料单体的粉末X射线衍射谱图;
图2为本发明所合成COF-DL602和原料单体的傅里叶红外谱图;
图3为本发明所合成COF-DL602的固体核磁谱图;
图4为本发明所合成COF-DL602的氮气吸脱附等温线;
图5为本发明所合成COF-DL602的孔径分布曲线;
图6为本发明所合成COF-DL602的热重分析曲线;
图7为本发明所合成COF-DL602在不同温度下的N2吸附等温线;
图8为本发明所合成COF-DL602在不同温度下的CO2吸附等温线;
图9为本发明所合成COF-DL602在不同温度下的H2吸附等温线;
图10为本发明所合成COF-DL602在不同温度下的CH4吸附等温线。
具体实施方式
以下结合附图和具体实施方式对本发明予以详细说明,此处所描述的实施例仅用于说明和解释本发明,但并不用于限定本发明。
以下实施例中的单体四(4-苯胺基)金刚烷(Org.Biomol.Chem.2009,7,4734)和四(对苯醛基)芘(J.Mater.Chem.2012,22,25409)可以采用文献中报道的方法合成得到。
实施例1
将7.5mg(0.015mmol)四面体构型的四(4-苯胺基)金刚烷(TAPA)和9.28mg(0.015mmol)四(对苯醛基)芘(TFPPy)加入到安瓿瓶中,加入1mL邻二氯苯,超声混合均匀,然后加入0.1mL(6mol/L)的醋酸水溶液,将安瓿瓶置于液氮中进行冷冻,抽真空并火焰封管,封管后置于烘箱中,升温至140℃加热5天。反应结束后,将所得固体转移至离心管中,用N,N-二甲基甲酰胺和四氢呋喃各离心洗涤5次,于温度90℃下加热真空干燥12小时得到固体产物,然后将所得到的固体产物置于索氏提取反应器中,用三氯甲烷作为溶剂,在温度100℃下加热提取5天。最后将索氏提取反应器中的固体产物于温度90℃下加热真空干燥12小时,即可得到13mg黄色固体粉末COF-DL602,产率83%,反应式如下式所示。
如图1所示,通过对比本发明所合成的COF-DL602和两种原料单体(TAPA和TFPPy)的粉末X射线衍射谱图,可以确定利用本发明的方法成功合成了一种新的共价有机框架材料。
如图2所示,通过对比本发明所合成的COF-DL602和两种原料单体(TAPA和TFPPy)的傅里叶红外谱图,可以发现COF-DL602的红外谱图中在1626cm-1处有明显的C=N键振动峰,说明了两种原料单体之间形成了亚胺键。
如图3所示,通过COF-DL602的固体核磁碳谱,可以观察到157ppm处的化学位移,同样证明了亚胺键连接方式的形成。
如图4所示,在温度77K下,COF-DL602的氮气吸脱附曲线属于典型的I型曲线,说明COF-DL602具有规整的微孔结构,其比表面积为:1467m2/g。
如图5所示,通过QSDFT方法计算得到COF-DL602的孔径分布和孔体积大小,COF-DL602的孔径主要分布在0.818nm,其孔体积为:0.895cm3/g。
如图6所示,通过热重分析可以发现,在氮气气氛下,COF-DL602可以稳定到540℃而不发生明显的分解,说明了COF-DL602具有很好的热稳定性。
如图7所示,在1bar的压强下,COF-DL602在温度273K和298K下吸附N2的质量分别为:7.66mg/g和6.91mg/g。
如图8所示,在1bar的压强下,COF-DL602在温度273K和298K下吸附CO2的质量分别为:176mg/g和89mg/g。
通过IAST方法计算得到COF-DL602在1bar的压强和温度273K和298K下,CO2/N2气体选择性分别为:15和51。
如图9所示,在1bar的压强下,COF-DL602在温度77K和87K下吸附H2的质量分别为:23.2mg/g和15.6mg/g。
如图10所示,在1bar的压强下,COF-DL602在温度273K和298K下吸附CH4的质量分别为:16mg/g和12mg/g。
实施例2
将7.5mg(0.015mmol)四面体构型的四(4-苯胺基)金刚烷和9.28mg(0.015mmol)四(对苯醛基)芘加入到安瓿瓶中,加入1mL邻二氯苯,超声混合均匀,然后加入0.1mL(3mol/L)的醋酸水溶液,将安瓿瓶置于液氮中进行冷冻,抽真空并火焰封管,封管后置于烘箱中,升温至140℃加热5天。反应结束后,将所得固体转移至离心管中,用N,N-二甲基甲酰胺和四氢呋喃各离心洗涤5次,于温度90℃下加热真空干燥12小时得到固体产物,然后将所得到的固体产物置于索氏提取反应器中,用三氯甲烷作为溶剂,在温度100℃下加热提取5天。最后将索氏提取反应器中的固体产物于温度90℃下加热真空干燥12小时,即可得到8.2mg黄色固体粉末COF-DL602,产率53%。
实施例3
将7.5mg(0.015mmol)四面体构型的四(4-苯胺基)金刚烷和9.28mg(0.015mmol)四(对苯醛基)芘加入到安瓿瓶中,加入0.8mL邻二氯苯和0.2mL均三甲苯,超声混合均匀,然后加入0.1mL(6mol/L)的醋酸水溶液,将安瓿瓶置于液氮中进行冷冻,抽真空并火焰封管,封管后置于烘箱中,升温至160℃加热5天。反应结束后,将所得固体转移至离心管中,用N,N-二甲基甲酰胺和四氢呋喃各离心洗涤5次,于温度90℃下加热真空干燥12小时得到固体产物,然后将所得到的固体产物置于索氏提取反应器中,用三氯甲烷作为溶剂,在温度100℃下加热提取5天。最后将索氏提取反应器中的固体产物于温度90℃下加热真空干燥12小时,即可得到12mg黄色固体粉末COF-DL602,产率77%。
实施例4
将15mg(0.03mmol)四面体构型的四(4-苯胺基)金刚烷和9.28mg(0.015mmol)四(对苯醛基)芘加入到安瓿瓶中,加入1mL邻二氯苯,超声混合均匀,然后加入0.1mL(6mol/L)的醋酸水溶液,将安瓿瓶置于液氮中进行冷冻,抽真空并火焰封管,封管后置于烘箱中,升温至160℃加热5天。反应结束后,将所得固体转移至离心管中,用N,N-二甲基甲酰胺和四氢呋喃各离心洗涤5次,于温度90℃下加热真空干燥12小时得到固体产物,然后将所得到的固体产物置于索氏提取反应器中,用三氯甲烷作为溶剂,在温度100℃下加热提取5天。最后将索氏提取反应器中的固体产物于温度90℃下加热真空干燥12小时,即可得到10mg黄色固体粉末COF-DL602,产率64%。
以上所述仅为本发明的优选实施例,并不能作为限制本发明的依据,对于本领域的技术研究人员来说,可以根据本发明的实施例对技术方案进行修改、等同替换、改进等,而所有这些变动都应属于本发明权利要求的保护范围之内。
Claims (9)
2.根据权利要求1所述基于金刚烷单元的三维共价有机框架材料的合成方法,其特征在于:所述四面体构型的四(4-苯胺基)金刚烷和四(对苯醛基)芘的摩尔比为1: (0.5-1)。
3.根据权利要求1所述基于金刚烷单元的三维共价有机框架材料的合成方法,其特征在于:所述的有机溶剂为邻二氯苯、体积比(4-9): 1的邻二氯苯和均三甲苯的混合溶剂、或体积比(7-10):1:2邻二氯苯和1,4-二氧六环及N,N-二甲基乙酰胺的混合溶剂;
有机溶剂用量为1.0-3.0 mL,相应的反应单体的总质量为17 mg-50 mg。
4.根据权利要求1所述基于金刚烷单元的三维共价有机框架材料的合成方法,其特征在于:所用的有机溶剂和醋酸水溶液的体积比为(6-10): 1。
5.根据权利要求1或4所述基于金刚烷单元的三维共价有机框架材料的合成方法,其特征在于:所用醋酸水溶液的浓度为3 M-9 M。
6.根据权利要求1所述基于金刚烷单元的三维共价有机框架材料的合成方法,其特征在于:所述加热晶化反应的温度为120-180 ℃ ;反应时间为3-30天。
7.根据权利要求1所述基于金刚烷单元的三维共价有机框架材料的合成方法,其特征在于:索氏提取采用的溶剂为三氯甲烷和四氢呋喃中的一种或二种。
8.一种权利要求1-7任一所述方法合成得到的基于金刚烷单元的三维共价有机框架材料。
9.一种权利要求8所述的共价有机框架材料作为气体吸附材料的应用,其特征在于:所述的共价有机框架材料用于吸附H2、CH4和CO2气体中的一种或二种以上。
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