CN109585887A - 一种染料@金属有机框架材料及其制备方法和用途 - Google Patents
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Abstract
本发明提供了一种染料@金属有机框架材料,其分子式为{[In3O L1.5(H2O)3](NO3)0.7(C16H7O10S3)0.1}·(C4H9NO)3·(CH3CN)6·(H2O)25,其中,C4H9NO为N,N'‑二甲基乙酰胺,C16H7O10S3为8‑羟基芘‑1,3,6‑三磺酸三钠盐,CH3CN为乙腈,该染料@金属有机框架材料的晶体结构属于立方晶系,空间群为晶胞参数为α=β=γ=90°,晶胞体积为本发明具有如下的有益效果:1、本发明通过选择合适的带质子载体的染料分子引入金属有机框架的孔中,制备出染料@金属有机框架材料作为作为质子传导材料和荧光检测器,同时提高质子导电率以及检测有机小分子的灵敏度。
Description
技术领域
本发明涉及一种具有染料@金属有机框架材料及其制备方法和用途,属于金属有机框架材料技术领域。
背景技术
质子交换膜燃料电池(Proton Exchange Membrane Fuel Cell,PEMFC)是一种不经燃烧直接将燃料的化学能转化为电能的发电装置,能量转化率高,且环境友好无污染,被认为是21世纪首选的高效清洁发电技术。质子交换膜(PEM)是PEMFC的关键材料之一,具有传导质子、隔离燃料和氧化剂的作用。目前研究和应用最多的是以Nafion为代表的全氟磺酸膜(PFSA),其在60~80℃温度范围及98%高湿度下质子导电性可高达10-1~10-2S·cm-1。然而随着研究不断的深入,PFSA的缺陷越来越明显,不仅对湿度有很大的依赖性,而且昂贵的铂基催化剂是必要品,更重要的一点是燃料渗透严重造成燃料的浪费及催化剂中毒,这些因素在很大程度上阻碍了燃料电池产业化进程。因此,开发新型的高性能质子交换膜已成为相关技术人员关注的焦点。
苯胺作为典型的芳香胺是不可缺少的化学前体,广泛应用于橡胶工业,染料中间体,医药等领域。然而,由于其严重的毒性和易致癌性质,即使在非常低的浓度下泄漏也会危害环境安全和人类健康,因此,快速有效地检测苯胺对于公共安全和环境保护来说是非常紧迫的。
发明内容
针对目前质子交换膜高湿度依赖性和运行温度范围窄等问题以及检测苯胺小分子灵敏度低等问题,本发明利用金属有机框架的多孔性及染料分子的光敏性,提供一种同时实现低湿度依赖性、宽温域高质子导电率和灵敏检测苯胺的染料@金属有机材料。
本发明是通过以下技术方案实现的:
本发明提供一种染料@金属有机框架材料,其分子式为{[In3O L1.5(H2O)3](NO3)0.7(C16H7O10S3)0.1}·(C4H9NO)3·(CH3CN)6·(H2O)25,其中,C4H9NO为N,N'-二甲基乙酰胺,C16H7O10S3为8-羟基芘-1,3,6-三磺酸三钠盐,CH3CN为乙腈,L为金属有机配体,结构式为该染料@金属有机框架材料的晶体结构属于立方晶系,空间群为晶胞参数为α=β=γ=90°,晶胞体积为其中每个铟离子通过四个不同配体的羧酸氧原子、一个水分子的氧原子以及一个μ3-O原子配位形成一个八面体的结构;三个金属离子和一个μ3-O原子以及来自不同配体的六个羧酸氧原子、三个水分子的氧原子形成一个三核金属的次级结构单元[In3O(COO)6],每个次级结构单元通过四齿的金属有机配体(L4-)连接形成三维结构,该染料@金属有机框架存在两种类型的孔道,孔的尺寸分别是和孔中存在无序的染料分子以及其他的客体分子。具体结构如图2所示。
一种如前述的染料@金属有机框架材料的制备方法,其包括如下步骤:
将8-羟基芘-1,3,6-三磺酸三钠盐,硝酸铟和4,4',4”,4”’-[1,4-亚苯双(吡啶-4,2,6-三取代)]四苯甲酸加入到N,N-二甲基乙酰胺和乙腈的混合溶剂中,超声分散10~20min后,加入稀硝酸;
密封后,在80~120℃下反应24~48h,将产物进行过滤、洗涤后,得到所述染料@金属有机框架材料。
作为优选方案,所述N,N-二甲基乙酰胺和乙腈的体积比为1:1~1:1.5。
作为优选方案,所述4,4',4”,4”’-[1,4-亚苯双(吡啶-4,2,6-三取代)]四苯甲酸、硝酸铟和8-羟基芘-1,3,6-三磺酸三钠盐摩尔比为3:10:0.1~3:10:5。
一种如前述的染料@金属有机框架材料在质子传导材料中的用途。
作为优选方案,所述质子传导材料包括第一电极、中间层和第二电极,所述中间层由染料@金属有机框架材料成型。
一种如前述的染料@金属有机框架材料在检测苯胺的荧光检测器中的用途。
与现有技术相比,本发明具有如下的有益效果:
1、本发明通过选择合适的带质子载体的染料分子引入金属有机框架的孔中,制备出染料@金属有机框架材料作为质子传导材料和荧光检测器,同时提高质子导电率以及检测有机小分子的灵敏度;
2、本发明合成的染料@金属有机框架材料,制备工艺简单,成本低,极大地满足实际应用中低湿度条件下高的质子导电率以及对苯胺小分子检测的敏感性,具有广阔的应用前景。
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是本发明合成的染料@金属有机框架材料的示意图;
图2是本发明中的In-MOF和HPTS@In-MOF材料的制备方法流程示意图;
图3是根据本发明中对比例1得到的In-MOF材料在不同温度下的尼奎斯特图;
图4是根据本发明中实施例1得到的HPTS@In-MOF材料在不同温度下的尼奎斯特图;
图5是根据本发明中实施例1得到的In-MOF和HPTS@In-MOF不同温度下导电率对比图;
图6是根据本发明中对比例1得到In-MOF在不同浓度的苯胺的I0/I曲线;
图7是根据本发明中实施例1得到HPTS@In-MOF在不同浓度的苯胺的的I0/I曲线。
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
本实施例涉及一种染料@金属有机框架材料的制备方法有机配体的制备方法,如图2所示,具体包括如下步骤:将0.1mmol硝酸铟,0.01mmol 8-羟基芘-1,3,6-三磺酸三钠盐(HPTS)和0.03mmol 4,4',4”,4”’-(1,4-亚苯双(吡啶-4,2,6-三取代))四苯甲酸加入到2mL1:1的N,N-二甲基乙酰胺和乙腈的混合溶剂,超声10~20分钟,加入少量稀硝酸;将上述溶液用玻璃容器密封,放置在烘箱,温度从室温加热到85℃;在上述温度85℃保温48h,取出玻璃瓶,冷却至室温;将玻璃瓶中的晶体过滤,用N,N-二甲基乙酰胺洗涤产品,产品在室温空气氛围干燥,得到干燥的紫红色的块状晶体(命名为HPTS@In-MOF)。
实施例2
本实施例涉及一种染料@金属有机框架材料的制备方法有机配体的制备方法,具体包括如下步骤:将0.1mmol硝酸铟,0.01mmol 8-羟基芘-1,3,6-三磺酸三钠盐(HPTS)和0.03mmol 4,4',4”,4”'-(1,4-亚苯双(吡啶-4,2,6-三取代))四苯甲酸加入到2mL 1:1的N,N-二甲基乙酰胺和乙腈的混合溶剂,超声10~20分钟,加入少量稀硝酸;将上述溶液用玻璃容器密封,放置在烘箱,温度从室温加热到90℃;在上述温度90℃保温24h,取出玻璃瓶,冷却至室温;将玻璃瓶中的晶体过滤,用N,N-二甲基乙酰胺洗涤产品,产品在室温空气氛围干燥,得到干燥的紫红色的块状晶体(命名为HPTS@In-MOF)。
实施例3
本实施例涉及一种染料@金属有机框架材料的制备方法有机配体的制备方法,具体包括如下步骤:将0.1mmol硝酸铟,0.01mmol 8-羟基芘-1,3,6-三磺酸三钠盐(HPTS)和0.03mmol 4,4',4”,4”'-(1,4-亚苯双(吡啶-4,2,6-三取代))四苯甲酸加入到2mL 1:1的N,N-二甲基乙酰胺和乙腈的混合溶剂,超声10~20分钟,加入少量稀硝酸;将上述溶液用玻璃容器密封,放置在烘箱,温度从室温加热到100℃;在上述温度100℃保温24h,取出玻璃瓶,冷却至室温;将玻璃瓶中的晶体过滤,用N,N-二甲基乙酰胺洗涤产品,产品在室温空气氛围干燥,得到干燥的紫红色的块状晶体(命名为HPTS@In-MOF)。
对比例1
本实施例涉及一种金属有机框架材料的制备方法有机配体的制备方法,具体包括如下步骤:将0.1mmol硝酸铟和0.03mmol 4,4',4”,4”'-(1,4-亚苯双(吡啶-4,2,6-三取代))四苯甲酸加入到2mL 1:1的N,N-二甲基乙酰胺和乙腈的混合溶剂,超声10~20分钟,加入少量稀硝酸;将上述溶液用玻璃容器密封,放置在烘箱,温度从室温加热到85℃;在上述温度85℃保温48h,取出玻璃瓶,冷却至室温;将玻璃瓶中的晶体过滤,用N,N-二甲基乙酰胺洗涤产品,产品在室温空气氛围干燥,得到干燥的黄色产品(命名为In-MOF)。
对比例2
本实施方案与实施例1的区别仅在于反应温度的从85℃变为80℃,得到该染料@金属有机框架的微晶样品。
对比例3
本实施方案与实施例1的区别仅在于反应温度的从85℃变为120℃,得到该染料@金属有机框架的粉末样品。
对比例4
本实施方案与实施例1的区别仅在于HPTS的物质的量从0.01mmol变为0.001mmol,得到该染料未负载的金属有机框架黄色样品。
对比例5
本实施方案与实施例1的区别仅在于HPTS的物质的量从0.01mmol变为0.05mmol,得到该染料@金属有机框架的紫红色粉末样品。
本发明利用SolartronAnalytical ModuLab 126阻抗仪测试In-MOF和HPTS@In-MOF的本进行无额外湿度条件下本征态质子传导测试,测试中观察到较好的半环出现(如图3和图4所示),两个产品在-40℃到90℃的温度范围内都具有较好的本征导电率。但染料分子进入MOF孔道的HPTS@In-MOF材料在整个温度范围具有更好的质子导率,并且在90℃电导率达到将近7.5×10-3S cm-1,接近同温度条件下是原始MOF材料质子导电率的五倍(图5),因此,染料分子进入MOF孔道能提高材料的质子导电率。
本发明利用Horiba FluoroMax-4fluorescence spectrometer荧光仪测试In-MOF和HPTS@In-MOF加入不同量的苯胺的荧光强度变化,从图6和图7可知,随着苯胺浓度逐渐增大,In-MOF和HPTS@In-MOF两个材料的相对荧光强度(I0/I)是逐渐增加的,说明两个材料对苯胺都响应,但从淬灭常数我们可知,染料分子进入MOF孔道的HPTS@In-MOF对苯胺的灵敏度比原始的In-MOF材料高,其Ksv常数达到5.82×104M-1。说明染料分子进入MOF的孔道能有效的提高检测苯胺的灵敏度。
本发明利用MOFs作为母版材料将染料分子封装进入孔道中形成染料@MOF材料,具有许多独特的优势1.MOFs材料具有结构规整的孔道能产生各种有趣的结构,为染料分子提供合适的平台;2.可自下而上,从分子水平上实现不同质子载体的染料分子进入不同孔道,达到结构与性能调控的关系;3.通过染料分子进入MOF的孔道能实现材料多功能应用,如荧光传感、质子导电等。4.制备工业简单,成本低,能有效解决常规路径无法决定的合成难题。
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 (7)
1.一种染料@金属有机框架材料,其特征在于,分子式为{[In3O L1.5(H2O)3](NO3)0.7(C16H7O10S3)0.1}·(C4H9NO)3·(CH3CN)6·(H2O)25,其中,C4H9NO为N,N'-二甲基乙酰胺,C16H7O10S3为8-羟基芘-1,3,6-三磺酸三钠盐,CH3CN为乙腈,L为金属有机配体,结构式为该染料@金属有机框架材料的晶体结构属于立方晶系,空间群为晶胞参数为α=β=γ=90°,晶胞体积为其中每个铟离子通过四个不同配体的羧酸氧原子、一个水分子的氧原子以及一个μ3-O原子配位形成一个八面体的结构;三个金属离子和一个μ3-O原子以及来自不同配体的六个羧酸氧原子、三个水分子的氧原子形成一个三核金属的次级结构单元[In3O(COO)6],每个次级结构单元通过四齿的金属有机配体连接形成三维结构,该染料@金属有机框架存在两种类型的孔道,孔的尺寸分别是和孔中存在无序的染料分子以及其他的客体分子。
2.一种如权利要求1所述的染料@金属有机框架材料的制备方法,其特征在于,包括如下步骤:
将8-羟基芘-1,3,6-三磺酸三钠盐,硝酸铟和4,4',4”,4”’-[1,4-亚苯双(吡啶-4,2,6-三取代)]四苯甲酸加入到N,N-二甲基乙酰胺和乙腈的混合溶剂中,超声分散10~20min后,加入稀硝酸;
密封后,在80~120℃下反应24~48h,将产物进行过滤、洗涤后,得到所述染料@金属有机框架材料。
3.如权利要求2所述的染料@金属有机框架材料的制备方法,其特征在于,所述N,N-二甲基乙酰胺和乙腈的体积比为1:1~1:1.5。
4.如权利要求2所述的染料@金属有机框架材料的制备方法,其特征在于,所述4,4',4”,4”’-[1,4-亚苯双(吡啶-4,2,6-三取代)]四苯甲酸、硝酸铟和8-羟基芘-1,3,6-三磺酸三钠盐摩尔比为3:10:0.1~3:10:5。
5.一种如权利要求1所述的染料@金属有机框架材料在质子传导材料中的用途。
6.如权利要求5所述的用途,其特征在于,所述质子传导材料包括第一电极、中间层和第二电极,所述中间层由染料@金属有机框架材料成型。
7.一种如权利要求1所述的染料@金属有机框架材料在检测苯胺的荧光检测器中的用途。
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