CN113045460A - 一种高核水簇的氢键有机框架材料及其制备方法 - Google Patents
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Abstract
本发明提供了一种通过调节疏水溶剂驱动构筑高核水簇的氢键有机框架材料的制备方法,通过该方法利用有机磺酸和胺类化合物设计出了两种通过氢键连接形成的具有不同三维立体结构的氢键有机框架材料,其结构式分别为C26H29NO5S,C24H25NO5S。本发明主要是调控疏水溶剂的比例构建,通过相同的小分子有机化合物构建不同的氢键有机框架结构,并且合成了一种全新的高核水簇有机框架材料,制作工艺简单,成本低。
Description
技术领域
本发明涉及一种高核水簇有机磺酸/铵的氢键有机框架材料,尤其涉及一种通过调控疏水溶剂来驱动构筑封装高核水簇的方法。
背景技术
自金属阳离子和有机分子配体构建多孔网络结构的金属有机框架材料和多孔配位聚合物被报道以来,利用有机小分子配体构建具有永久孔道结构的晶体材料引起了人们的强烈兴趣和关注,并被广泛应用于选择性气体分离/储存,质子传导,催化,分子识别,光学和生物医学等领域。氢键有机框架材料的的设计紧随其后,在2010年提出。自提出的10多年来,各类有机配体构建的HOFs材料层出不穷,缤纷各异,如何通过控制反应条件和有机配体定向设计合成出具有目标结构和性能的氢键有机框架化合物(HOFs)成为很多科研人员所面临的挑战之一。
发明内容
本发明提供了一种调控疏水溶剂来驱动构筑封装高核水簇的方法,可以有效解决上述问题。
本发明是通过以下技术方案实现的:
一种高核水簇的氢键有机框架材料,其特结构式为C24H25NO5S。
一种如前述的高核水簇的氢键有机框架材料的制备方法,其包括如下步骤:
将磺酸芳香烃和胺基芳香烃溶解于有机溶剂A中,形成反应液,将所述反应液中的有机溶剂A挥发彻底,得到无色块状晶体;
将所述无色块状晶体用有机溶剂B溶解后,加入疏水性有机溶剂,溶解完全后,挥发结晶,得到所述高核水簇的氢键有机框架材料。
作为优选方案,所述的磺酸芳香烃和胺基芳香烃的比例为1:(1~2)。
作为优选方案,所述磺酸芳香烃为1,5-萘二磺酸。
作为优选方案,所述胺基芳香烃选自二苯基甲胺和三苯基甲胺中的一种或两种。
作为优选方案,所述有机溶剂A选自甲醇中的一种或两种。
作为优选方案,所述有机溶剂B选自甲醇中的一种或两种。
作为优选方案,所述疏水性有机溶剂选自苯,甲苯,二甲苯,硝基苯,环己烯,环己烷,三甲苯中的至少一种。
作为优选方案,所述的甲醇、水、疏水溶剂按照体积比为500:2:25。
本发明的有益效果在于:
本发明采用调节疏水性溶剂的量来驱动构筑封装高核水簇的有机框架材料,具体操作在于用亲水溶剂生长氢键有机框架材料后,通过添加疏水性溶剂的比例驱动构筑封装高核水簇的有机框架材料对原始材料进行结构上的改造。有效解决了目前定向构建氢键有机框架材料的设计问题,同时具有工艺简单,成本低,具有相对高的产率。基于上述原理,本发明合成了一系列的有机共晶材料,这对实现设计构建氢键有机框架材料具有极大的借鉴意义。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述,本发明的其它特征、目的和优点将会变得更明显:
图1是本发明中调控疏水溶剂来驱动构筑封装高核水簇的流程示意图;
图2为本实施例制备的高核水簇有机共晶材料C24H25NO5S的结构示意图;
图3为高核水簇有机共晶材料C24H25NO5S的XRD图谱。
图4为高核水簇有机共晶材料C24H25NO5S的水蒸气吸附图谱。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
请参照图1,将1,5-萘二磺酸(1.0g,3.47mmol),三苯甲胺(1.75g,6.94mmol)加入100ml甲醇溶液中,超声使其完全溶解,室温下缓慢挥发结晶,得到无色块状晶体C26H29NO5S,产量为1.5g,产率为85.88%;
称取20mg的晶体1加入5ml甲醇中,超声使其完全溶解,量取20μl水和250μl甲苯加入澄清溶液,室温下缓慢挥发,得无色棒状晶体C24H25NO5S,产量为12mg,产率为63.8%。本发明设计调控疏水溶剂来驱动构筑封装高核水簇的方法,可以调控氢键有机框架的配位方式,实现有机配体的重新组装获得新的氢键有机框架材料。
表征:
请参照图3,图3为高核水簇有机共晶材料的XRD图谱;图中曲线2为实验合成的材料的XRD图谱;图中曲线1为由单晶结构数据通过Mercury软件模拟的该有机共晶的XRD图谱,由图3可见,曲线1和曲线2基本吻合,说明合成的材料为纯相,没有杂质。
由图4可知,高核水簇有机共晶C24H25NO5S在较低的大气压下(0.3个大气压),就可以发生水蒸气吸附行为,吸附量达到了40cm3/g,作为干燥剂和水存储材料具有广阔的前景,并且具有工艺简单,成本低,合成产率高的优点。
对比例
本对比例与实验例的区别仅仅在于,在合成原料晶体C26H29NO5S后,添加同样比例的亲水溶剂乙酸乙酯,得到的是白色沉淀,无法得到高核水簇有机共晶C24H25NO5S,这一实验证明了疏水性溶剂在调节驱动构筑高核水簇的氢键有机框架材料中起到了决定性作用。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
Claims (9)
1.一种高核水簇的氢键有机框架材料,其特征在于,结构式为C24H25NO5S。
2.一种如权利要求1所述的高核水簇的氢键有机框架材料的制备方法,其特征在于,包括如下步骤:
将磺酸芳香烃和胺基芳香烃溶解于有机溶剂A中,形成反应液,将所述反应液中的有机溶剂A在室温下挥发彻底,得到无色块状晶体;
将所述无色块状晶体用有机溶剂B溶解后,加入疏水性有机溶剂,溶解完全后,室温下挥发结晶,得到所述高核水簇的氢键有机框架材料。
3.如权利要求1所述的高核水簇的氢键有机框架材料的制备方法,其特征在于,所述的磺酸芳香烃和胺基芳香烃的比例介于1:(1~2)。
4.如权利要求2或3所述的高核水簇的氢键有机框架材料的制备方法,其特征在于,所述磺酸芳香烃为1,5-萘二磺酸。
5.如权利要求2或3所述的高核水簇的氢键有机框架材料的制备方法,其特征在于,所述胺基芳香烃选自二苯基甲胺和三苯基甲胺中的一种或两种。
6.如权利要求2所述的高核水簇的氢键有机框架材料的制备方法,其特征在于,所述有机溶剂A选自甲醇。
7.如权利要求2所述的高核水簇的氢键有机框架材料的制备方法,其特征在于,所述有机溶剂B选自甲醇。
8.如权利要求2所述的高核水簇的氢键有机框架材料的制备方法,其特征在于,所述疏水性有机溶剂选自苯,甲苯,二甲苯,硝基苯,环己烯,环己烷,三甲苯中的至少一种。
9.如权利要求2所述的高核水簇的氢键有机框架材料的制备方法,其特征在于,所述的甲醇、水、疏水溶剂按照体积比为500:2:25。
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US11479482B1 (en) | 2022-05-31 | 2022-10-25 | King Fahd University Of Petroleum And Minerals | Hydrogen-bonded organic framework (HOF) for water uptake |
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