CN112608490B - 硫醚功能化的芘基共价有机框架材料及其制备方法和应用 - Google Patents
硫醚功能化的芘基共价有机框架材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于共价有机框架材料领域,具体涉及硫醚功能化的芘基共价有机框架材料及其制备方法和应用。本发明将2,5‑双(2‑(乙硫基)乙氧基)对苯二甲酰肼和1,3,6,8‑四‑(对醛基苯基)‑芘加入到溶剂体系中,反应制得硫醚功能化的芘基共价有机框架材料。本发明合成方法所用到的设备和化学试剂易于获取,工艺操作简便,适用性强,工业应用价值高,合成产率相对较高,本发明制备的芘基共价有机框架材料对可见光具有良好的响应,在光催化分解水制氢领域有良好的潜在应用价值,易于推广利用。
Description
技术领域
本发明属于共价有机框架材料领域,具体涉及一种硫醚功能化的芘基共价有机框架材料及其制备方法和应用。
背景技术
共价有机框架材料(COF)是一种以动态共价键连接形成的新型晶态有机多孔材料。与传统的多孔碳材料或MOFs材料相比,具有低密度和高稳定性的优点。随着全球能源需求的快速增长,寻求清洁和可再生能源作为消耗化石燃料的替代品变得比以往任何时候都更加紧迫。由于氢的高能量密度和无碳排放,氢能被认为是解决全球能源危机的最具前景的能源之一。光催化分解水是一项极为重要的技术进步过程,可以利用丰富的太阳能直接实现质子还原,获得清洁的氢能有助于缓解甚至解决目前的环境问题和能源问题。因此基于氢能源发展起来的光催化制氢技术逐步受到研究学者们的关注与重视。传统的催化制氢材料多数集中在无机半导体材料上,一些轻质元素组成的微孔材料少有报道。
CN110229345A公开了一种含β酮烯胺结构的共价有机框架材料及其制备方法与应用,具体公开了将芘基二苯胺和2,4,6-三甲酰基均苯三酚在有机溶剂中混合均匀,加入弱酸性催化剂,在溶剂热条件下发生可逆的席夫碱反应和不可逆的烯醇-酮式互变异构反应,得到包含β酮烯胺结构的共价有机框架材料。该技术方案的共价有机框架材料主要是为了满足电化学储能器件的实际需要,具有高比电容值、高循环稳定性的,但是难以用于光催化制氢。
CN111607051A公开了一种三维荧光共价有机框架材料及其制备方法与应用,以六甲基联苯醛类衍生物与一系列芘基胺类衍生物为原料,邻二氯苯与均三甲苯为溶剂,乙酸为催化剂,溶剂热反应若干天。反应结束后,依次用DMF,THF抽滤洗涤,索氏提取24小时后真空干燥得黄色粉末。该技术方案的共价有机框架材料主要是以基于位阻效应的六甲基联苯四醛和具有荧光性质的芘基四胺作为构筑单体,合成出的“Turn-on”型三维荧光共价有机框架具有丰富的空腔结构以及共轭的三维骨架,在荧光传感领域展现出良好的应用前景,但是难以用于光催化制氢。
综上所述,现有技术仍缺乏一种能够满足光催化制氢应用的共价有机框架材料。
发明内容
针对现有技术的改进需求,本发明提供了一种硫醚功能化的芘基共价有机框架材料,硫醚功能化的芘基共价有机框架材料具有较好的可见光响应,合适的能带位置,有较好的光催化制氢活性,特别是能够通过金属掺杂等方法提高其光催化制氢活性,能够应用于光催化制氢。
为实现上述目的,按照本发明的一个方面,提供了一种硫醚功能化的芘基共价有机框架材料,结构式如式(1)所示:
其中,所述式(1)中苯环上连接的“……”表示省略的重复结构单元。
按照本发明的另一方面,提供了一种硫醚功能化的芘基共价有机框架材料的制备方法,将2,5-双(2-(乙硫基)乙氧基)对苯二甲酰肼和1,3,6,8-四-(对醛基苯基)-芘加入到溶剂体系中,反应制得前面所述的芘基共价有机框架材料。
作为优选,具体包括以下步骤:
(1)将2,5-双(2-(乙硫基)乙氧基)对苯二甲酰肼和1,3,6,8-四-(对醛基苯基)-芘加入到溶剂体系,超声混合均匀;
(2)将反应体系抽真空后密封;
(3)加热反应生成黄色固体沉淀,反应温度为100-120℃,反应时间为3-5天;
(4)过滤分离得到沉淀物,洗涤干燥后,得到硫醚功能化的芘基共价有机框架材料。
作为优选,所述溶剂为邻二氯苯、无水乙醇、醋酸三者的混合。
作为优选,所述邻二氯苯、所述无水乙醇与所述醋酸的体积比为(5-10):(5-10):(1-2)。
作为优选,所述步骤(2)中抽真空时,先将反应体系通过液氮浴冷冻,然后解冻,抽真空结束后进行火焰密封。
作为优选,所述洗涤包括第一次洗涤和第二次洗涤,所述第一次洗涤为无水四氢呋喃和无水乙醇洗涤若干次,所述第二次洗涤为二氯甲烷和N,N-二甲基甲酰胺洗涤若干次。
作为优选,所述干燥为80-100℃真空干燥12-24h。
按照本发明的另一方面,提供了硫醚功能化的芘基共价有机框架材料的应用,所述应用包括作为催化剂用于光催化分解水制氢。
作为优选,所用牺牲供体为三乙醇胺,助催化剂为Au纳米颗粒,所述助催化剂的前驱体为氯金酸。
本发明的有益效果有:
(1)本发明通过使用2,5-双(2-(乙硫基)乙氧基)对苯二甲酰肼和1,3,6,8-四-(对醛基苯基)-芘为反应原料,在邻二氯苯、无水乙醇、醋酸溶剂体系下溶剂热反应合成得到一种硫醚功能化的芘基共价有机框架材料,制备的硫醚功能化的芘基共价有机框架材料具有较好的可见光响应,合适的能带位置,其合成产率相对较高,对可见光具有良好的响应,在光催化分解水制氢领域有良好的潜在应用价值。
(2)本发明合成方法所用到的设备和化学试剂易于获取,工艺操作简便,适用性强,工业应用价值高,易于推广利用。
附图说明
图1为实施例1所得S4-COF的合成示意图;
图2为实施例1所得S4-COF的X射线粉末衍射图;
图3为实施例1所得S4-COF和合成单体的傅里叶变换红外光谱图;
图4为实施例1所得S4-COF的固体紫外吸收光谱图;
图5为实施例1所得S4-COF在纯水条件下光催化循环制氢测试图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例
本发明实施例提供了一种硫醚功能化的芘基共价有机框架材料,结构式如式(1)所示:
其中,所述式(1)中苯环上连接的“……”表示省略的重复结构单元。
本发明实施例硫醚功能化的芘基共价有机框架材料的制备方法,将2,5-双(2-(乙硫基)乙氧基)对苯二甲酰肼和1,3,6,8-四-(对醛基苯基)-芘加入到溶剂体系中,反应制得前面所述的芘基共价有机框架材料。以下为具体实施例。
实施例1
一种硫醚功能化的芘基共价有机框架材料,通过以下方法制备而成:
(1)将2,5-双(2-(乙硫基)乙氧基)对苯二甲酰肼(19.52mg,48.5μmol)和1,3,6,8-四-(对醛基苯基)-芘(15mg,24.25μmol)加入到1.1mL邻二氯苯、无水乙醇和醋酸溶剂体系中,邻二氯苯、无水乙醇和醋酸的体积之比为5:5:1,并置于5mL Pyrex管中,Pyrex管体长20cm,颈长1cm,超声处理3分钟,混合均匀。
(2)将Pyrex管在液氮浴中冷冻,解冻后抽真空至0mbar的内部压力并进行火焰密封。
(3)将Pyrex管置于120℃的烘箱中反应3天,生成黄色固体。
(4)抽滤收集沉淀物,用无水四氢呋喃和无水乙醇洗涤三次,再用二氯甲烷和N,N-二甲基甲酰胺洗涤三次。将黄色粉末在80℃真空干燥24h,得到一种硫醚功能化的芘基共价有机框架材料,记为S4-COF,称量为33.5mg,计算分离产率为69%。
本实施例制备的硫醚功能化的芘基共价有机框架材料S4-COF的合成示意图见图1。
测试实施例
1.X射线粉末衍射测试,将实施例1的S4-COF进行测试,测试结果如图2所示。S4-COF的X射线粉末衍射图在3.2°,4.2°,6.5°,9.8°和24.5°处显示峰形,它们分别对应(110),(200),(220),(330)和(001)晶面。在各种可能的堆积模式中,AA堆积模式是能量中结构最稳定的堆积形式。实验观察到的X射线粉末衍射曲线与结构拟合的AA堆积模式相匹配。
2.傅里叶变换红外光谱测试,将实施例1的S4-COF进行测试,测试结果如图3所示。S4-COF和合成单体的傅里叶变换红外光谱用于验证各官能团的伸缩振动。与酰肼单体和芘基单体相比,S4-COF的傅立叶变换红外光谱显示1,3,6,8-四-(对醛基苯基)-芘中-CHO拉伸带(1697cm-1)消失并且在1662cm-1处出现了C=O键的伸缩振动。此外,与C=N键相关的特征伸缩振动模式出现在1601cm-1和1226~1203cm-1附近,这表明成功形成了亚胺官能团。
3.固体紫外吸收光谱测试,将实施例1的S4-COF进行测试,测试结果如图4所示。固体紫外吸收光谱图显示,S4-COF具有较宽的可见光吸收范围,表现出很强的可见光收集能力。
应用实施例
将实施例1制备的S4-COF应用于光催化循环制氢,具体如下所述。
将20mg实施例1制备的S4-COF作为光催化剂悬浮在含有三乙醇胺(10vol%)作为牺牲电子给体的超纯水(50mL)中,滴加1.0wt%Au(前驱体为氯金酸制备)作为助催化剂,在超声浴中分散5分钟,在可见光(≥420nm)的照射下,进行光催化分解纯水制氢,循环实验进行4次,每次循环4小时。通过GC气相色谱分析析出的H2量。
S4-COF在纯水条件下光催化循环制氢测试图见图5。由图5知,S4-COF的光催化分解水制氢总量在第一次运行至4小时表现为110.2μmol,并且在可见光照射(λ≥420nm)下进行循环实验稳定测试至16小时制氢产量仍可高达80μmol以上。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (9)
2.根据权利要求1所述的制备方法,其特征在于,具体包括以下步骤:
(1)将2,5-双(2-(乙硫基)乙氧基)对苯二甲酰肼和1,3,6,8-四-(对醛基苯基)-芘加入到溶剂体系,超声混合均匀;
(2)将反应体系抽真空后密封;
(3)加热反应生成黄色固体沉淀,反应温度为100-120℃,反应时间为3-5天;
(4)过滤分离得到沉淀物,洗涤干燥后,得到硫醚功能化的芘基共价有机框架材料。
3.根据权利要求1或2所述的制备方法,其特征在于,所述溶剂为邻二氯苯、无水乙醇、醋酸三者的混合。
4.根据权利要求3所述的制备方法,其特征在于,所述邻二氯苯、所述无水乙醇与所述醋酸的体积比为(5-10):(5-10):(1-2)。
5.根据权利要求1所述的制备方法,其特征在于,所述步骤(2)中抽真空时,先将反应体系通过液氮浴冷冻,然后解冻,抽真空结束后进行火焰密封。
6.根据权利要求2所述的制备方法,其特征在于,所述洗涤包括第一次洗涤和第二次洗涤,所述第一次洗涤为无水四氢呋喃和无水乙醇洗涤若干次,所述第二次洗涤为二氯甲烷和N,N-二甲基甲酰胺洗涤若干次。
7.根据权利要求2所述的制备方法,其特征在于,所述干燥为80-100℃真空干燥12-24h。
8.根据权利要求1-7任一项所述的制备方法制备而成的硫醚功能化的芘基共价有机框架材料的应用,其特征在于,所述应用包括作为催化剂用于光催化分解水制氢。
9.根据权利要求8所述的硫醚功能化的芘基共价有机框架材料的应用,其特征在于,所用牺牲供体为三乙醇胺,助催化剂为Au纳米颗粒。
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