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CN106810571B - 一种基于yiii的稀土簇金属有机骨架材料及其制备方法和应用 - Google Patents

一种基于yiii的稀土簇金属有机骨架材料及其制备方法和应用 Download PDF

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CN106810571B
CN106810571B CN201710065918.8A CN201710065918A CN106810571B CN 106810571 B CN106810571 B CN 106810571B CN 201710065918 A CN201710065918 A CN 201710065918A CN 106810571 B CN106810571 B CN 106810571B
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韩正波
黄鑫磊
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Weifang Huawei Environmental Protection New Materials Center LP
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Abstract

本发明涉及一种基于YIII的稀土簇金属有机骨架材料及其制备方法和应用。采用的技术方案是：将Y(NO3)3，1,3,5‑三(4‑羧基苯基)苯，邻氟苯甲酸，N,N‑二甲基甲酰胺和水，加入容器中，于常温下，搅拌20‑40分钟；将容器密封后放入烘箱中，于温度378K±10K下，保持1‑2天；缓慢冷却到室温，得到无色透明棒状晶体；洗涤、过滤并干燥，得目标产物。本发明所制备的基于YIII的稀土簇金属有机骨架材料可以作为荧光探针高效选择性传感丙酮。

Description

一种基于YIII的稀土簇金属有机骨架材料及其制备方法和 应用
技术领域
本发明涉及一种基于YIII的稀土簇金属有机骨架材料，具体的说，涉及一种具有荧光探针功能的基于YIII的稀土簇金属有机骨架材料的制备及其应用。
背景技术
近年来，金属有机骨架材料(MOFs)是化学和材料科学中上升最迅速的领域之一。金属有机骨架材料(MOFs)是一类新兴的多孔材料，是由金属节点或金属簇与有机连接体组成的多孔晶态材料。具有较大的比表面积，孔隙率，高稳定性，可裁剪性等优点。由于金属和配体的组合方式无穷无尽，而且金属有机框架(MOFs)材料的设计受配位的金属离子、多齿配体的结构特征、金属/配体的比例以及抗衡离子的影响，稍微改变这些因素都可能产生新的网络结构。由于它们的结构和功能具有可调控性，每年有成千上万新的MOFs被合成出来，开发其在气体的分离存储、磁性、催化、光学材料、药物传输等领域的潜在应用价值。
传统的无机和有机荧光材料已经被各国研究人员广泛地探索，无机和有机基团能分别展现出不同特点的荧光性质。而无机和有机基团相互作用又可以产生新的荧光性质。一般地金属有机框架(MOFs)材料是由无机金属离子和有机配体共同构筑的，因此，金属有机框架 (MOFs)材料作为荧光材料是个较好的选择。金属有机框架(MOFs)材料的荧光性质主要受到结构的特点、金属离子的配位环境、孔表面性质的影响。丙酮在工业上主要作为溶剂，用于炸药、塑料、橡胶、纤维、等行业中，由于易燃、易挥发，化学性质较活泼，因此，定性的荧光检测丙酮对于日常生产的安全的处理具有重要意义。
发明内容
本发明的目的是利用九核钇簇作为金属节点，利用1,3,5-三(4-羧基苯基)苯作为有机配体，在一定的温度下，利用溶剂热的方法合成一种基于YIII的稀土簇金属有机骨架材料。
本发明的另一目的是提供一种基于YIII的稀土簇金属有机骨架材料作为荧光探针检测丙酮的方法。
本发明采用的技术方案是：一种基于YIII的稀土簇金属有机骨架材料，包括以下合成步骤：
1)将Y(NO3)3，1,3,5-三(4-羧基苯基)苯，邻氟苯甲酸，N,N-二甲基甲酰胺，水加入容器中，于常温下，搅拌20-40分钟；
2)将容器密封后放入烘箱中，于378K±10K下，保持1-2天；优选的，升温速率为 2-6K·min-1。
3)缓慢冷却到室温，得到无色透明棒状晶体；优选的，缓慢冷却到室温的降温速率为 4-8K·min-1，并在室温下静置至少一天。洗涤，过滤并干燥，得目标产物。
本发明的有益效果是：本发明所制备的一种基于YIII的稀土簇金属有机骨架材料可作为多功能材料应用于荧光分子探针领域。所制备的一种基于YIII的稀土簇金属有机骨架材料可以作为荧光探针对丙酮进行检测。本发明的一种基于YIII的稀土簇金属有机骨架材料的制备方法简单，具有很大的应用前景。
附图说明
图1是基于YIII的稀土簇金属有机骨架材料的PXRD图。
图2a是基于YIII的稀土簇金属有机骨架材料一种笼子示意图。
图2b是基于YIII的稀土簇金属有机骨架材料一种笼子示意图。
图2c是基于YIII的稀土簇金属有机骨架材料一种笼子示意图。
图2d是基于YIII的稀土簇金属有机骨架材料孔道示意图。
图3是基于YIII的稀土簇金属有机骨架材料的固体荧光光谱图。
图4是基于YIII的稀土簇金属有机骨架材料中配体1,3,5-三(4-羧基苯基)苯的固体荧光光谱图。
图5是基于YIII的稀土簇金属有机骨架材料在不同溶剂中的荧光强度柱状图。
图6是基于YIII的稀土簇金属有机骨架材料的甲醇悬浊液加入10-200ppm丙酮的荧光光谱图。
具体实施方式
实施例1 一种基于YIII的稀土簇金属有机骨架材料
将0.0225mmol的Y(NO3)3，0.015mmol的1,3,5-三(4-羧基苯基)苯，0.0675mmol的邻氟苯甲酸，2ml的N,N-二甲基甲酰胺(DMF)，0.5ml的水加入体积为5ml的玻璃瓶中，并且常温条件搅拌30分钟。将玻璃瓶密封好放入烘箱中。加热使烘箱的温度从室温达到378 K，升温速率为5K·min-1，并保持温度在此条件下保温36小时。以5K·min-1的降温速率缓慢冷却到室温，并在室温下静置至少一天，得到无色透明棒状晶体；用N,N’-二甲基甲酰胺(DMF)溶液洗涤、过滤并在空气中干燥，即为目标产物基于YIII的稀土簇金属有机骨架材料，产率为68％。
本发明合成的基于YIII的稀土簇金属有机骨架材料的PXRD检测，结果如图1，合成晶体的PXRD衍射图与模拟图的相关峰的位置相互吻合的很好，说明合成的基于YIII的稀土簇金属有机骨架材料是纯相。结构为：其属于六方晶系，空间群为P63/mmc。分子式为： (DMA+)2[Y9(μ3-OH)8(μ2-OH)3((O2C–C6H4)3C6H3)6]·n(solv)x。该化合物是由九核[Y9(μ3-OH)8(μ2-OH)3(O2C–)18]作为节点，由三羧酸配体桥联而成的三维结构。阳离子[(CH3)2NH2]+作为抗衡离子位于该MOF的孔道中。每个1,3,5-三(4-羧基苯基)苯配体与三个Y3+离子配位，六个Y3+离子与四个来自于1,3,5-三(4-羧基苯基)苯的羧基上的氧以及三个μ3-OH和一个μ2-OH配位，其余三个位点的配位模块是由四个羧基上的氧和两个μ2-OH配位。沿b-轴方向，该结构有三种不同的笼子结构，笼子的尺寸为并且存在一个孔道(图2a-图2b)。
实施例2 一种基于YIII的稀土簇金属有机骨架材料的发光
方法：以实施例1制备一种基于YIII的稀土簇金属有机骨架材料进行发光性能实验。
在室温下，对YIII的稀土簇金属有机骨架材料和1,3,5-三(4-羧基苯基)苯配体，进行了固体荧光光谱学测试。从图3可以看出，YIII的稀土簇金属有机骨架材料在290nm为激发波长激发下，对产生的发射曲线在350-500nm范围内收集，在375处存在一个荧光发射峰。从图4固体荧光光谱图中，可以看出，1,3,5-三(4-羧基苯基)苯配体在285nm为激发波长激发下，对产生的发射曲线在350-500nm范围内收集，在385nm处存在一个强而且宽的荧光发射特征峰。从中可以看出YIII的稀土簇金属有机骨架材料的发射带和1,3,5-三(4-羧基苯基)苯的荧光发射带一致，所以YIII的稀土簇金属有机骨架材料的发光行为属于其配体1,3,5-三(4- 羧基苯基)苯发光，是由于π–π*转移作用引起的。
1)1mg的一种基于YIII的稀土簇金属有机骨架材料，分别放入5mL的甲醇、乙醇、N,N- 二甲基甲酰胺、N,N-二甲基乙酰胺、乙腈、丙酮、四氢呋喃、二氯甲烷、三氯甲烷、 1,4-二氧六环中。经过超声溶解，用荧光分光光度计检测溶液中一种基于YIII的稀土簇金属有机骨架材料的荧光强度。实验结果如图5，在甲醇、乙醇、N,N-二甲基甲酰胺、 N,N-二甲基乙酰胺、乙腈、丙酮、四氢呋喃、二氯甲烷、三氯甲烷、1,4-二氧六环中，只有丙酮对YIII的稀土簇金属有机骨架材料的荧光强度产生淬灭，而加入其他溶剂，只引起YIII的稀土簇金属有机骨架材料较小程度的荧光强度的减弱。以上结果表明，YIII的稀土簇金属有机骨架材料可以通过明显的荧光淬灭现象选择性识别丙酮。
2)进一步探究了丙酮的检测极限，制备1×10-4M的基于YIII的稀土簇金属有机骨架材料的甲醇溶液。
取混合溶液5ml，分别加入10ppm、20ppm、30ppm、40ppm、80ppm、120 ppm、160ppm、200ppm的丙酮。用荧光分光光度计检测混合溶液荧光强度的变化。结果如图6所示，当丙酮的浓度为200ppm时，YIII的稀土簇金属有机骨架材料的荧光强度淬灭效率达到92.5％，表明几乎淬灭完全。这说明本发明的YIII的稀土簇金属有机骨架材料可以高灵敏度检测丙酮。

Claims (6)

1.基于YIII的稀土簇金属有机骨架材料作为荧光探针在检测丙酮中的应用，其特征在于，所述的基于YIII的稀土簇金属有机骨架材料的制备方法包括如下步骤：
1）将Y(NO3)3，1,3,5-三(4-羧基苯基)苯，邻氟苯甲酸，N,N-二甲基甲酰胺，水加入容器中，于常温下，搅拌20-40分钟；
2）将容器密封后放入烘箱中，于378 K±10 K下，保持1-2天；
3）缓慢冷却到室温，得到棒状晶体；洗涤，过滤并干燥，得目标产物。
2.根据权利要求1所述的应用，其特征在于方法如下：于有机溶剂中加入基于YIII的稀土簇金属有机骨架材料，然后加入含有丙酮的溶液，超声分散，进行荧光检测。
3.根据权利要求2所述的应用，其特征在于：所述的有机溶剂是甲醇。
4.根据权利要求1所述的应用，其特征在于：步骤1)中，N,N-二甲基甲酰胺，水的体积比为4:1。
5.根据权利要求1所述的应用，其特征在于：步骤2）中，将容器密封后放入烘箱中，升温速率为2-6 K·min -1。
6.根据权利要求1所述的应用，其特征在于：步骤3）中，所述的缓慢冷却到室温的降温速率为4-8 K·min -1，并在室温下静置至少一天。
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