CN105693697B - 基于8-羟基喹啉的有机配体、有机框架及其制备方法 - Google Patents
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Abstract
本发明公开了基于8‑羟基喹啉的有机配体、有机框架及其制备方法,基于8‑羟基喹啉的有机配体L,其化学结构式为:将上述有机配体L和二价金属盐溶于N,N‑二甲基甲酰胺的水溶液中,调节溶液pH值使溶液为弱酸性后,将溶液在120℃下72‑76小时,然后经48‑50小时降至20‑35℃后,制得所述金属有机框架。本发明以8‑羟基喹啉有机配体作为合成基底,制备得到两例不同的金属有机框架结构,金属有机框架具有大的孔穴结构,稳定性好,该金属有机框架具有一个较大孔穴,在储气、小分子吸附有较好的性能,可以吸附在室温下吸附CO2、CH4等气体小分子。室温下Zn‑MOF对CO2最大吸附量达到76.1cm3/g,CH4最大吸附量达到7.1cm3/g,Co‑MOF对CO2最大吸附量达到64.9cm3/g,CH4最大吸附量达到13.2cm3/g。
Description
技术领域
本发明属于无机-有机纳米材料制备技术领域,具体涉及基于8-羟基喹啉的有机配体、有机框架及其制备方法。
背景技术
金属有机框架结构(Metal-organic Framework,MOF)是近年来研究的热点,是通过金属离子或者金属簇与有机配体之间相互作用,组装形成多孔的材料,与传统的有孔材料相比,MOF具有多孔性,较大的比表面积和框架内孔体积,在储气、载药、化学传感、催化以及富集分离检测等领域得到很多的研究及应用。
目前随着二氧化碳的排放量的增加,温室效应日益严重,如何减少空气中CO2的含量已成为世界性的环境问题。由于MOFs材料具有可调节的孔径,CO2相比其他气体具有更小的动力学直径(0.33nm),因此设计具有合适孔径的MOFs材料用于CO2特异性吸附分离是减少温室气体的一种途径,但这在实际的设计和合成过程中仍有很多的困难。在多数情况下,MOFs材料的孔径比吸附的气体大,但由于动力筛分效应仍然可以特异性吸附CO2,如Mn(HCO3)2的孔笼直径大小为0.55nm,孔窗大小为0.45nm,实验证实其在78K时对N2和Ar几乎没有吸附作用,在195K时特异性吸附CO2。其对CO2的选择性吸附主要是由于材料比较小的孔窗限制了N2和Ar进入材料的孔道,而CO2则可以进入。而目前MOF材料在室温下对气体小分子的吸附能力普遍较差。如2003年Yaghi小组首次报道了介孔MOFs材料在氢气存储方面的应用,在78K条件下吸附氢气4.5%,在室温2MPa气压下吸附氢气1%。所以,现有的有机金属框架材料在低温高压下对气体的吸附作用较好,这样就限制了有机金属框架在气体吸附中的应用。
发明内容
本发明的目的为解决现有技术中存在的以上弊端,提供一种基于8-羟基喹啉的有机配体、有机框架及其制备方法。
为实现上述目的,本发明采用如下技术方案:
一种基于8-羟基喹啉的有机配体L,其化学结构式为:
一种基于二价金属的金属有机框架,由上述有机配体L和二价金属盐制备而来。
上述金属有机框架的制备方法,包括如下步骤:
将上述有机配体L和二价金属盐溶于N,N-二甲基甲酰胺的水溶液中,调节溶液pH值使溶液为弱酸性后,将溶液在115-125℃下恒温72-76小时,然后经48-50小时降至20-35℃后,制得所述金属有机框架。
调节溶液pH值使溶液为弱酸性的目的是使配体能够与金属离子更易成键,将溶液在120℃左右下恒温72h以上时间的目的是保持合适的成键温度,为反应提供能量,将溶液经48h以上时间降至室温的目的是析出晶体,更好地生成单晶。
优选的,所述有机配体L与二价金属盐的摩尔比为1:1。
优选的,所述N,N-二甲基甲酰胺的水溶液中N,N-二甲基甲酰胺和水的摩尔比为1:1-4。在此溶液比例下,可以有效提高有机配体L和盐的溶解度,并能够在最后析出单晶。
优选的,将有机配体L和二价金属盐溶于N,N-二甲基甲酰胺的水溶液中后,调节溶液的pH值为4-6。
优选的,所述二价金属盐为高氯酸锌或硝酸钴。
进一步优选的,所述二价金属盐为高氯酸锌,制备的基于Zn(Ⅱ)的金属有机框架Zn-MOF,其结构式为[Zn C20H12N3O3]n,n为非零的自然数。
该金属有机框架Zn-MOF的单晶结构图1所示,Zn-MOF结晶为单斜晶系,属于P121/c空间群,每个不对称单元中均有一个Zn金属中心,每个Zn为六配位,分别两个吡啶上的N配位,一个8-羟基喹啉的N配位,一个8-羟基喹啉的O配位,甲酸的两个O配位。
进一步优选的,所述二价金属盐为硝酸钴,制备的基于Co(Ⅱ)的金属有机框架Co-MOF,其结构式为[Co C20H12N3O3]n,n为非零的自然数。其单晶结构图2所示。
所述的金属有机框架在吸附气体小分子中的应用,尤其是在室温常压下吸附二氧化碳中的应用。
本发明的有益效果为:
(1)本发明以8-羟基喹啉有机配体作为合成基底,制备得到两例不同的金属有机框架结构,金属有机框架具有大的孔穴结构,稳定性好,该金属有机框架具有一个较大孔穴,在储气、小分子吸附有较好的性能,可以在室温下吸附CO2、CH4等气体小分子。室温下20-35℃,Zn-MOF对CO2最大吸附量达到76.1cm3/g,CH4最大吸附量达到7.1cm3/g,Co-MOF对CO2最大吸附量达到64.9cm3/g,CH4最大吸附量达到13.2cm3/g。其吸附曲线图8、9所示。
(2)本发明的反应条件温和,反应时间短,制备方法简单易行。
附图说明
图1本发明的Zn-MOF的单晶结构图;
图2本发明的Co-MOF的单晶结构图;
图3本发明的Zn-MOF、Co-MOF的X射线粉末衍射图;
图4本发明的Zn-MOF的红外谱图;
图5本发明的Cu-MOF的红外谱图;
图6本发明的Zn-MOF的TGA谱图;
图7本发明的Co-MOF的TGA谱图;
图8本发明的Zn-MOF的气体吸附曲线图;
图9本发明的Co-MOF的气体吸附曲线图。
具体实施方式
结合实施例对本发明作进一步的说明,应该说明的是,下述说明仅是为了解释本发明,并不对其内容进行限定。
实施例1:基于Zn(Ⅱ)的金属有机框架Zn-MOF
以8-羟基喹啉为母体的有机配体L的制备方法,包括如下步骤:
N2保护下,向三口圆底烧瓶中加入5,7-二溴-8-对甲氧基吡啶喹啉14.0g(10mmol),4-吡啶硼酸3.2g(26mmol),无水碳酸钠13.6g(128mmol),四三苯基膦钯0.8g(0.6mmol),苯、乙醇、水各40ml的混合液(超声除氧15min),加热回流30h。待反应液冷却后倒入水中,用二氯甲烷萃取两次,萃取液旋干,得粗品,柱层析得得白色固体3.4g,产率67.20℅。
该金属有机框架的制备方法,包括如下步骤:
将有机配体L(11.7mg 0.03mmol)、高氯酸锌(11.1mg 0.03mmol)置于N,N-二甲基甲酰胺:水=1:1溶液中,pH调至5。置于5mL小试管中,120℃条件下恒温72小时,经48小时降温至室温,即得黄色正方形块状单晶Zn-MOF。其结构式为[Zn C20H12N3O3]n,n为非零的自然数;产量15mg,产率78.5%(以L为准)。Zn-MOF的单晶结构示意图如图1所示,X射线粉末衍射图如图3所示,红外谱图如图4所示,TGA谱图如图6所示。
将新制备Zn-MOF(80mg)在常压下200℃加热2小时,除尽其中的客体水分子,在真空状态下70℃加热8小时,获得一个无客体的样品,进行气体吸附性能表征,室温常压下对CO2最大吸附量达到76.1cm3/g,CH4最大吸附量达到7.1cm3/g,在已知MOF材料里吸附量较大。附曲线图8所示。目前吸附技术大部分采用如图所示的低压区吸附方法(最高压力约为1.2个大气压,另外也有采用高压吸附,如20-50个大气压不等),现有的有机金属框架结构,在常温常压下对二氧化碳的吸附量在60cm3/g以下,所以,本发明的有机金属框架结构,且在室温下常压下对二氧化碳具有较高的吸附量。
实施例2:基于Co(Ⅱ)的金属有机框架
该金属有机框架的制备方法,包括如下步骤:
将硝酸钴替换高氯酸锌重复Zn-MOF的合成,得紫红色块状单晶Co-MOF,其结构式为[Zn C20H12N3O3]n,n为非零的自然数;产量21.0mg,产率84.0%。Co-MOF的单晶结构示意图如图2所示,X射线粉末衍射图如图3所示,红外谱图如图5所示,TGA谱图如图7所示。
将新制备Co-MOF(80mg)在常压下200℃加热2小时,除尽其中的客体水分子,在真空状态下70℃加热8小时,获得一个无客体的样品,进行气体吸附性能表征,室温常压下对CO2最大吸附量达到64.9cm3/g,CH4最大吸附量达到13.2cm3/g,在已知MOF材料里吸附量较大。其吸附曲线图9所示。
上述虽然结合附图对本发明的具体实施方式进行了描述,但并非对本发明保护范围的限制,所属领域技术人员应该明白,在本发明的技术方案的基础上,本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。
Claims (4)
1.一种金属有机框架的制备方法,其特征在于:包括如下步骤: 将有机配体L 和二价金属盐溶于N, N-二甲基甲酰胺的水溶液中,有机配体L为一种基于8-羟基喹啉的有机配体,结构式为:
,
调节溶液pH 值使溶液为弱酸性后,将溶液在115-125℃恒温72-76 小时,然后经48-50小时降至20-35℃后, 制得所述金属有机框架; 有机配体L 与二价金属盐的摩尔比为1:1;N, N-二甲基甲酰胺的水溶液中N, N-二甲基甲酰胺和水的摩尔比为1:1-4;有机配体L 和二价金属盐溶于N, N-二甲基甲酰胺的水溶液中后,调节溶液的pH 值为4-6;
所述二价金属盐为高氯酸锌或硝酸钴。
2.权利要求1所述的制备方法制备的金属有机框架,其特征在于:所述二价金属盐为高氯酸锌,制备的金属有机框架为基于Zn(Ⅱ)的金属有机框架。
3.权利要求1所述的制备方法制备的金属有机框架,其特征在于:所述二价金属盐为硝酸钴,制备的金属有机框架为基于Co(Ⅱ)的金属有机框架。
4.权利要求2或3所述的金属有机框架在室温下吸附CO2或CH4中的应用。
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"以芴、8-羟基喹啉和联苯二酚类有机配体构建的MOFs的离子识别与分离、热致变色及催化氧化性质的研究";马建平;《中国博士学位论文全文数据库 工程科技I辑》;20130815;B014-634 |
"金属有机框架材料的研究进展";翟睿等;《色谱》;20140228;第32卷(第2期);第107-116页 |
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