CN108117513B - 三维联吡啶功能化的有机多孔材料及其合成方法和应用 - Google Patents
三维联吡啶功能化的有机多孔材料及其合成方法和应用 Download PDFInfo
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Abstract
本发明公开了一种三维联吡啶功能化的有机多孔材料及其合成方法和应用，该材料的合成方法为：在有机溶剂中，将四面体构型的四(4‑苯胺基)金刚烷和2,2’‑二联吡啶‑5,5’‑二甲醛均匀混合，然后加入催化剂醋酸水溶液，经过加热晶化、离心洗涤和加热真空干燥，可得到三维有机多孔材料BiPy‑Ad。本发明方法得到的BiPy‑Ad材料具有较高的比表面积，且呈现出微/介孔性质，并在气体(如H2、CO2及CH4)的吸附实验中，表现出了较大容量的气体吸附能力。因此，BiPy‑Ad材料可以作为一种优异的气体吸附材料，应用于气体存储。
Description
技术领域
本发明属于有机多孔材料领域，具体涉及三维联吡啶功能化的有机多孔材料及其合成方法和应用。
背景技术
以分子筛为代表的传统多孔材料具有大的比表面积、规整的孔道结构和活性位点，目前已成为精细化工、石油化工和日用化工等领域中一类重要的功能材料，，然而随着人类社会和技术的飞速发展，人们亟需开发新型多孔材料以满足人们在材料领域和能源领域日益增长的需求。在新型多孔材料中，无机-有机杂化多孔材料尤其是金属有机框架材料以及有机多孔材料在近年来发展迅速，其中，有机多孔材料作为一类由轻质元素通过共价键形成的稳定多孔材料，不仅具有较大的比表面积，而且具有较低的骨架密度及孔道、功能可裁剪的特征，近年来也已被广泛应用于吸附、催化和光电材料等领域。
吡啶基团是一种功能化的结构单元，在荧光探针、有机光电、材料化学、配位化学、多相催化等领域中有着广泛的应用。吡啶基团的结构与苯环相似，具有芳香性，适合用于构筑有机多孔材料，而且吡啶环上的氮原子有一对孤对电子，呈一定的碱性，即能够与金属原子进行配位，也能作为氢键给体。因此，将吡啶骨架引入有机多孔材料中，在功能化有机多孔材料的合成与应用方面具有重要意义。
发明内容
本发明目的在于提供一种三维联吡啶功能化的有机多孔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：
一种三维联吡啶功能化的有机多孔材料，该材料的结构式为：
一种三维联吡啶功能化的有机多孔材料的合成方法，包括如下步骤：
将四面体构型的四(4-苯胺基)金刚烷(TAPA)和2,2’-二联吡啶-5,5’-二甲醛(2,2’-BPy DCA)加入到安瓿瓶中，加入有机溶剂，超声混合均匀，然后加入醋酸水溶液作为催化剂，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、离心洗涤和加热真空干燥，即可得到三维联吡啶功能化的有机多孔材料BiPy-Ad。
优选的，四(4-苯胺基)金刚烷和2,2’-二联吡啶-5,5’-二甲醛的摩尔比为1:(2-3.5)；最佳摩尔比为：1:2。
优选的，所用有机溶剂为邻二氯苯、1,4-二氧六环、邻二氯苯/均三甲苯的混合溶剂、邻二氯苯/1,4-二氧六环的混合溶剂；最佳溶剂为：1,4-二氧六环。
优选的，所用的有机溶剂和醋酸水溶液的体积比为(5-10):1；最佳体积比为：10:1。
优选的，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。
优选的，所述反应的温度为120-180℃；最佳反应温度为：140℃。
优选的，所述反应的时间为3-30天；最佳反应时间为：5天。
上述方法合成得到的三维联吡啶功能化的有机多孔材料可应用于多种气体的吸附存储，具体用于吸附H2、CH4和CO2气体。
本发明具有如下优点：
1、本发明利用含有联吡啶的单元构筑了一种新型三维有机多孔材料；在有机多孔材料研究领域中，提供了一种新的合成方法；
2、通过本发明方法得到的BiPy-Ad材料具有较高的比表面积，且呈现出微/介孔性质；
3、BiPy-Ad材料在气体H2、CO2及CH4的吸附实验中，表现出了较大容量的气体吸附能力，拓展了有机多孔材料在气体吸附领域的应用。
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BiPy-Ad材料的粉末X射线衍射谱图；
图2为本发明所合成BiPy-Ad材料的氮气吸脱附等温线；
图3为本发明所合成BiPy-Ad材料的孔径分布图；
图4为本发明所合成BiPy-Ad材料在77K下的H2吸附等温线；
图5为本发明所合成BiPy-Ad材料在273K下的CO2吸附等温线；
图6为本发明所合成BiPy-Ad材料在273K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2,2’-二联吡啶-5,5’-二甲醛(Org.Lett.,2007,9,5641)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6.4mg(0.03mmol)2,2’-二联吡啶-5,5’-二甲醛(2,2’-BPy DCA)加入到安瓿瓶中，加入1mL1,4-二氧六环，超声混合均匀，然后加入0.1mL 6M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，依次用N,N-二甲基甲酰胺和四氢呋喃各离心洗涤3次，然后用四氢呋喃浸泡12小时，抽滤，所得固体于90℃下加热真空干燥12小时，即可得到8.7mg浅黄色固体粉末BiPy-Ad，产率68％，反应式如下式所示。
如图1所示，粉末X射线衍射谱图显示本发明所合成的BiPy-Ad材料为无定型材料。
如图2所示，温度77K下的氮气吸脱附曲线表明本发明所合成的BiPy-Ad材料具有较高的比表面积(795m2/g)。
如图3所示，通过NLDFT方法计算得到孔径分布图，BiPy-Ad材料呈现出微/介孔性质，孔径分布主要在3.6nm。
如图4所示，在1bar的压强下，BiPy-Ad材料在温度77K下吸附H2的质量为：1.56mg/g。
如图5所示，在1bar的压强下，BiPy-Ad材料在温度273K下吸附CO2的质量为：150.46mg/g。
如图6所示，在1bar的压强下，BiPy-Ad材料在温度273K下吸附CH4的质量为：19.85mg/g。
实施例2
将7.5mg(0.015mmol)四面体构型的四(4-苯胺基)金刚烷(TAPA)和6.4mg(0.03mmol)2,2’-二联吡啶-5,5’-二甲醛(2,2’-BPy DCA)加入到安瓿瓶中，加入1mL1,4-二氧六环，超声混合均匀，然后加入0.1mL 3M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，依次用N,N-二甲基甲酰胺和四氢呋喃各离心洗涤3次，然后用四氢呋喃浸泡12小时，抽滤，所得固体于90℃下加热真空干燥12小时，即可得到6.0mg浅黄色固体粉末BiPy-Ad，产率47％。经检测：为无定型材料，BET比表面积为603m2/g，孔径分布主要在3.6nm。
实施例3
将7.5mg(0.015mmol)四面体构型的四(4-苯胺基)金刚烷(TAPA)和6.4mg(0.03mmol)2,2’-二联吡啶-5,5’-二甲醛(2,2’-BPy DCA)加入到安瓿瓶中，加入0.8mL邻二氯苯和0.2mL1,4-二氧六环，超声混合均匀，然后加入0.1mL 6M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，依次用N,N-二甲基甲酰胺和四氢呋喃各离心洗涤3次，然后用四氢呋喃浸泡12小时，抽滤，所得固体于90℃下加热真空干燥12小时，即可得到7.1mg浅黄色固体粉末BiPy-Ad，产率55％。经检测：为无定型材料，BET比表面积为650m2/g，孔径分布主要在3.6nm。
实施例4
将7.5mg(0.015mmol)四面体构型的四(4-苯胺基)金刚烷(TAPA)和6.4mg(0.03mmol)2,2’-二联吡啶-5,5’-二甲醛(2,2’-BPy DCA)加入到安瓿瓶中，加入1mL1,4-二氧六环，超声混合均匀，然后加入0.1mL 6M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，依次用N,N-二甲基甲酰胺和四氢呋喃各离心洗涤3次，然后用四氢呋喃浸泡12小时，抽滤，所得固体于90℃下加热真空干燥12小时，即可得到6.4mg浅黄色固体粉末BiPy-Ad，产率50％。经检测：为无定型材料，BET比表面积为647m2/g，孔径分布主要在3.6nm。
实施例5
将7.5mg(0.015mmol)四面体构型的四(4-苯胺基)金刚烷(TAPA)和8.0mg(0.0375mmol)2,2’-二联吡啶-5,5’-二甲醛(2,2’-BPy DCA)加入到安瓿瓶中，加入1mL1,4-二氧六环，超声混合均匀，然后加入0.1mL 6M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，依次用N,N-二甲基甲酰胺和四氢呋喃各离心洗涤3次，然后用四氢呋喃浸泡12小时，抽滤，所得固体于90℃下加热真空干燥12小时，即可得到8.3mg浅黄色固体粉末BiPy-Ad，产率65％。经检测：为无定型材料，BET比表面积为671m2/g，孔径分布主要在3.6nm。
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)
1.一种三维联吡啶功能化的有机多孔材料的合成方法，其特征在于具体操作如下：
将四面体构型的四(4-苯胺基)金刚烷(TAPA)和2,2’-二联吡啶-5,5’-二甲醛(2,2’-BPy DCA)加入到安瓿瓶中，加入有机溶剂1,4-二氧六环或体积比为1-6：1邻二氯苯和1,4-二氧六环的混合溶剂，超声混合均匀，然后加入醋酸水溶液作为催化剂，将安瓿瓶置于液氮中进行冷冻，抽真空并火焰封管，加热至120℃～180℃晶化3-30天，离心洗涤和加热真空干燥，即可得到三维联吡啶功能化的有机多孔材料；所述材料的结构式为：
2.根据权利要求1所述三维联吡啶功能化的有机多孔材料的合成方法，其特征在于：所述四(4-苯胺基)金刚烷和2,2’-二联吡啶-5,5’-二甲醛的摩尔比为1:2-3.5；所述有机溶剂体积与相应的反应单体的总质量的比为0.5-2.5：7-40mL/mg；所用的有机溶剂和醋酸水溶液的体积比为5-10:1；所用醋酸水溶液的浓度为3-9M。
3.根据权利要求1所述三维联吡啶功能化的有机多孔材料的合成方法，其特征在于：所述四(4-苯胺基)金刚烷和2,2’-二联吡啶-5,5’-二甲醛的摩尔比为1:2。
4.根据权利要求1所述三维联吡啶功能化的有机多孔材料的合成方法，其特征在于：所述的有机溶剂为1,4-二氧六环。
5.根据权利要求1所述三维联吡啶功能化的有机多孔材料的合成方法，其特征在于：所用的有机溶剂和醋酸水溶液的体积比为10:1。
6.根据权利要求1所述三维联吡啶功能化的有机多孔材料的合成方法，其特征在于：所用醋酸水溶液浓度为6M。
7.根据权利要求1所述三维联吡啶功能化的有机多孔材料的合成方法，其特征在于：所述反应温度为140℃。
8.根据权利要求1所述三维联吡啶功能化的有机多孔材料的合成方法，其特征在于：所述反应时间为5天。
9.一种如权利要求1所述的三维联吡啶功能化的有机多孔材料的应用，其特征在于有机多孔材料用于吸附H2、CH4和CO2中的一种或二种以上。
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