CN110862549A - 一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料及其制备方法 - Google Patents
一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料及其制备方法 Download PDFInfo
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Abstract
本发明属于金属‑有机骨架晶体材料技术领域,具体涉及一种基于延胡索酸及4,4'‑联吡啶的三维金属‑有机骨架晶体材料及其制备方法。是将延胡索酸、4,4’‑联吡啶、硝酸锌、水与乙醇、甲醇或丙酮置于具聚四氟乙烯内衬的高压反应釜中,用NaOH调节pH为9,超声混匀,保持120℃反应三天,自然冷却到室温。经过过滤、洗涤后得到无色块状晶体。本发明是一种新型具有规则孔道结构的三维金属‑有机骨架晶体材料,具有较高的比表面积、孔容和良好的热稳定性,可以有效提高甲烷的吸附和存储量。该材料在药物合成、气体存储、捕集、分离,药物输送,光、电、磁,选择性催化,分子识别以及手性拆分等诸多领域都具有应用价值。
Description
技术领域
本发明属于金属-有机骨架晶体材料技术领域,具体的说,涉及一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料及其制备方法。
背景技术
金属-有机骨架晶体材料属于超分子化合物的一种,是晶体工程理论与超分子化学相结合的产物。它具有无机和有机的两部分优点,变化有机配体的可以使此类分子筛结构实现多样化的结构和可调控的孔道,从而做到定向设计。关于种新型分子功能材料的研究横跨了晶体工程学、材料化学、拓扑学、无机化学、有机化学、超分子化学、配位化学、物理化学、等多个领域。此材料具有类沸石分子筛般孔道规则的晶态结构,还具备比传统多孔材料更高的比表面积,另外包含有机成分使其结构得到了可剪裁性、可设计性、可调节孔道尺寸和功能化孔道表面等特点,在主–客体化学,药物合成、气体存储、捕集、分离,药物输送,光、电、磁学科,选择性催化,分子识别以及手性拆分等诸多领域都表现出色。近年来,金属-有机骨架晶体材料已成为新功能化材料研究的热点之一。最近,一些金属-有机骨架晶体材料已经成功实现商业化。
延胡索酸,又名富马酸、紫堇酸或地衣酸可作为酸度调节剂、酸化剂、抗氧化助剂、腌制促进剂、香料使用,并对抑菌防霉有重要作用。医学将其用于治疗严重银屑病,还可用于还可以帮助防止多发性硬化症等。
4,4’-联吡啶是常用的医药及有机合成中间体,且可用于测定铁含量及液晶材料。而金属锌具有良好的光电磁性能以及促进人体的生长发育及增强免疫力等能力。
有鉴于此,本案发明人特提出了基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料及其制备方法,既保留了各配体本身的化学及药理性质,又形成了具有规则孔道结构的三维金属-有机骨架晶体材料结构在药物合成、气体存储、捕集、分离,药物输送,光、电、磁,选择性催化,分子识别以及手性拆分等诸多领域都具有应用价值。
发明内容
为了克服背景技术中存在的问题,本发明提供了一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料及其制备方法,既保留了各配体本身的化学及药理性质,又形成了具有规则孔道结构的三维金属-有机骨架晶体材料结构在药物合成、气体存储、捕集、分离,药物输送,光、电、磁,选择性催化,分子识别以及手性拆分等诸多领域都具有应用价值。
为实现上述目的,本发明是通过如下技术方案实现的:
所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料以延胡索酸为配体A、4,4’-联吡啶为配体B与金属锌配位组成该金属-有机骨架晶体材料基本结构单元;在此金属-有机骨架晶体材料基本结构单元结构当中包含两个二价锌离子、四个延胡索酸配体和两个4,4’-联吡啶配体;其中,两个锌离子均采取六配位的形式,与每个锌离子分别配位的四个氧原子和一个氮原子分别来自由四个延胡索酸配体提供的四个单齿配位的羧基氧原子、一个4,4’-联吡啶配体提供的杂环氮原子,还有一个配位键由两个锌离子直接配位形成;两个4,4’-联吡啶配体相互垂直沿ab平面与锌离子配位并伸展,四个延胡索酸配体与锌离子配位并向四个方向延伸,最终形成了延c轴方向具有规则孔道结构的三维金属-有机骨架材料晶体结构,其化学分子式为:C18H13N2O8.50Zn2,属于单斜晶体(monoclinic,),空间群为:C 1 2/m 1(12),晶胞参数为:α=90°,β=105.938(3)°,γ=90°,Z=4。该金属-有机骨架晶体材料的是一种孔结构高度有序、孔径为0.38nm-3.6nm的三维规则孔道体系微孔类分子筛,Langmuir比表面积为1025m 2/g,总孔容0.389cm 3/g。从而表现出优异的分子扩散与吸附性能,吸附容量大,并且变温、变压条件下甲烷的吸附和存储量高。
进一步的,所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料由延胡索酸配体及4,4’-联吡啶配体与金属锌离子按2:2:1的摩尔比组合而成。其三维网络结构Langmuir比表面积为1025m2/g,总孔容0.389cm3/g。
所述的一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料制备方法,其特征在于包括如下步骤:
(1)将摩尔比0.5:0.5:1~4:4:1的延胡索酸配体、4,4’-联吡啶配体和硝酸锌以及有机溶剂,一并加入到高压反应釜中;
(2)将高压反应釜置于超声器上,室温超声混匀1-4小时;
(3)搅拌停止后,将高压反应釜置于40~120℃烘箱中放置10~40小时后取出,降到室温后有块状无色晶体析出,即为基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料
进一步的,步骤(1)所述的有机溶剂选自甲醇、乙醇、异丙醇、乙酸乙酯、丙酮、乙腈中的一种或几种。
进一步的,步骤(1)反应温度为40~120℃。
进一步的,步骤(2)的超声混匀为2小时;
进一步的,所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料在药物合成、气体存储、捕集、分离中的应用。
进一步的,所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料在药物输送中的应用.
进一步的,所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料在光、电、磁领域中的应用.
进一步的,所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料在选择性催化、分子识别、手性拆分领域中的应用。
本发明的有益效果:
本发明制备的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料既保留了各配体本身的化学及药理性质,又形成了具有规则孔道结构的三维金属-有机骨架晶体材料结构在药物合成、气体存储、捕集、分离,药物输送,光、电、磁,选择性催化,分子识别以及手性拆分等诸多领域都具有应用价值。
附图说明
图1:本发明金属-有机骨架晶体材料结构单元示意图;
图2:本发明金属-有机骨架晶体材料显微镜结构图;
图3:本发明金属-有机骨架晶体材料的空间三维网络图;
图4:本发明金属-有机骨架晶体材料模拟得到XRD谱图;
图5:本发明金属-有机骨架晶体材料的TG图;
图6:在77K、0~1atm条件下本发明金属-有机骨架晶体材料的氮气吸附等温线;
图7:在298K、323K;0~10bar条件下本发明金属-有机骨架晶体材料的金属有机框架材料的甲烷存储能力等温线。
具体实施方式
为了使本发明的目的、技术方案和有益效果更加清楚,下面将对本发明的优选实施例进行详细的说明,以方便技术人员理解。
本发明选用延胡索酸为配体A,4,4’-联吡啶为配体B与金属锌配位并在水与乙醇、甲醇或丙酮等溶剂中制备得到的一种新型具有规则孔道结构的三维金属-有机骨架晶体材料。
延胡索酸与4,4’-联吡啶是有机羧酸是临床药物及药物合成前体,分子式分别为:C4H4O4;C10H8N2,其结构式如式a,b所示。
所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料以延胡索酸为配体A、4,4’-联吡啶为配体B与金属锌配位组成该金属-有机骨架晶体材料基本结构单元;在此金属-有机骨架晶体材料基本结构单元结构当中包含两个二价锌离子、四个延胡索酸配体和两个4,4’-联吡啶配体;其中,两个锌离子均采取六配位的形式,与每个锌离子分别配位的四个氧原子和一个氮原子分别来自由四个延胡索酸配体提供的四个单齿配位的羧基氧原子、一个4,4’-联吡啶配体提供的杂环氮原子,还有一个配位键由两个锌离子直接配位形成;两个4,4’-联吡啶配体相互垂直沿ab平面与锌离子配位并伸展,四个延胡索酸配体与锌离子配位并向四个方向延伸,最终形成了延c轴方向具有规则孔道结构的三维金属-有机骨架材料晶体结构,其化学分子式为:C18H13N2O8.50Zn2,属于单斜晶体(monoclinic,),空间群为:C 1 2/m 1(12),晶胞参数为: α=90°,β=105.938(3)°,γ=90°,Z=4。所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料由延胡索酸配体及4,4’-联吡啶配体与金属锌离子按2:2:1的摩尔比组合而成。其晶体结构表征如下:
晶体结构测定采用Bruker Apex II CCD衍射仪,于296(2)K下,用经石墨单色化的MoKα射线以ω扫描方式收集衍射点,收集的数据通过SAINT程序还原并用SADABS方法进行半经验吸收校正。结构解析和精修分别采用SHELXTL程序的SHELXS和SHELXL完成,通过全矩阵最小二乘方法对F 2进行修正得到全部非氢原子的坐标及各向异性参数。所有氢原子在结构精修过程中被理论固定在母原子上,赋予比母原子位移参数稍大(C–H,1.2或O/N–H,1.5倍)的各向同性位移参数。详细的晶体测定数据见表1,结构单元示意图如图1,
基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料显微镜结构图如图2,基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料的空间三维网络图如图3,基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料的模拟粉末衍射图如图4。
表1共晶体主要晶体学数据
基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料的热稳定性、低温氮气吸附及甲烷气体吸附表征:
在0℃到600℃范围内氮气环境下对基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料进行的热重分析。图5是TG测试图,从图中可以看出,基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料可以稳定到380℃;在50-260℃范围内发生第一次失重,失重比例为31.99%,可归属于客体分子与端基配位分子的失去。而在260℃-380℃范围内发生骨架坍塌而失重34.22%,最终分解产物剩余33.69%。
将基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料在100℃下真空活化3个小时,并在77K的温度下对活化好的样品进行低温氮气吸附,结果如图6所示。并测得基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料的BET面积754.4m2/g,相应的朗格缪尔面积为1025m2/g,总孔容0.389cm3/g。
图7是基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料在298K和323K对甲烷的吸附曲线。从图7中可以看出甲烷的吸附量随着压强的增加而增加。当压强增加到10bar时,该材料在298K下吸附了2.02mmol/g的甲烷。当温度升高到323K时,甲烷吸附量为1.57mmol/g。
制备方法实施例1:一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料的制备方法:
0.2mmol延胡索酸、0.2mmol 4,4’-联吡啶和0.1mmol硝酸锌加入3ml水和3ml乙醇组成的混合溶剂并置于具聚四氟乙烯内衬的高压反应釜中,室温超声混匀2小时;超声停止后,将高压反应釜置于80℃烘箱中放置20小时后取出,降到室温后有块状无色晶体析出,摩尔收率87%。
制备方法实施例2:基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料的制备方法:
0.2mmol延胡索酸、0.2mmol 4,4’-联吡啶和0.1mmol硝酸锌加入3ml水和3ml甲醇组成的混合溶剂并置于具聚四氟乙烯内衬的高压反应釜中,室温超声混匀2小时;超声停止后,将高压反应釜置于80℃烘箱中放置20小时后取出,降到室温后有块状无色晶体析出,摩尔收率85%。
制备方法实施例3:基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料的制备方法:
0.2mmol延胡索酸、0.2mmol 4,4’-联吡啶和0.1mmol硝酸锌加入3ml水和3ml丙酮组成的混合溶剂并置于具聚四氟乙烯内衬的高压反应釜中,室温超声混匀2小时;超声停止后,将高压反应釜置于80℃烘箱中放置20小时后取出,降到室温后有块状无色晶体析出,摩尔收率84%。
最后说明的是,以上优选实施例仅用于说明本发明的技术方案而非限制,尽管通过上述优选实施例已经对本发明进行了详细的描述,但本领域技术人员应当理解,可以在形式上和细节上对其作出各种各样的改变,而不偏离本发明权利要求书所限定的范围。
Claims (9)
1.一种基于延胡索酸及4,4'-联吡啶的三维金属-有机骨架晶体材料,其特征在于:所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料以延胡索酸为配体A、4,4’-联吡啶为配体B与金属锌配位组成该金属-有机骨架晶体材料基本结构单元;在此金属-有机骨架晶体材料基本结构单元结构当中包含两个二价锌离子、四个延胡索酸配体和两个4,4’-联吡啶配体;其中,两个锌离子均采取六配位的形式,与每个锌离子分别配位的四个氧原子和一个氮原子分别来自由四个延胡索酸配体提供的四个单齿配位的羧基氧原子、一个4,4’-联吡啶配体提供的杂环氮原子,还有一个配位键由两个锌离子直接配位形成;两个4,4’-联吡啶配体相互垂直沿ab平面与锌离子配位并伸展,四个延胡索酸配体与锌离子配位并向四个方向延伸,最终形成了延c轴方向具有规则孔道结构的三维金属-有机骨架材料晶体结构,其化学分子式为:C18H13N2O8.50Zn2,属于单斜晶体(monoclinic,),空间群为: C 12/m 1 (12) ,晶胞参数为:a=13.4229(11) Å,b= 11.4760(9) Å,c=14.1021(12) Å,α=90°,β= 105.938 (3)°,γ= 90°, V = 2088.8 Å3, Z =4。
2.根据权利要求1所述的一种基于延胡索酸及4,4'-联吡啶的三维金属-有机骨架晶体材料,其特征在于:所述的基于延胡索酸及4,4'-联吡啶的三维金属-有机骨架晶体材料由延胡索酸配体及4,4’-联吡啶配体与金属锌离子按2:2:1的摩尔比组合而成,其三维网络结构Langmuir比表面积为 1025 m2/g,总孔容0.389 cm3/g。
3.根据权利要求1所述的一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料制备方法,其特征在于包括如下步骤:
(1)将摩尔比 0.5:0.5:1~4:4:1的延胡索酸配体、4,4’-联吡啶配体和硝酸锌以及有机溶剂,一并加入到高压反应釜中;
(2)将高压反应釜置于超声器上,室温超声混匀1-4小时;
(3) 搅拌停止后,将高压反应釜置于40~120℃烘箱中放置10~40小时后取出,降到室温后有块状无色晶体析出,即为基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料。
4.根据权利要求3所述的一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料制备方法,其特征在于:步骤(1)所述的有机溶剂选自甲醇、乙醇、异丙醇、乙酸乙酯、丙酮、乙腈中的一种或几种。
5.根据权利要求3所述的一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料制备方法,其特征在于:步骤(1)反应温度为40~120℃。
6.根据权利要求1所述的一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料,其特征在于:所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料在药物合成、气体存储、捕集、分离中的应用。
7.根据权利要求1所述的一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料,其特征在于:所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料在药物输送中的应用。
8.根据权利要求1所述的一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料,其特征在于:所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料在光、电、磁领域中的应用。
9.根据权利要求1所述的一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料,其特征在于:所述的基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料在选择性催化、分子识别、手性拆分领域中的应用。
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