CN114805912A - 一种用于k+电化学传感器的mof复合多孔敏感膜的制备方法 - Google Patents

一种用于k+电化学传感器的mof复合多孔敏感膜的制备方法 Download PDF

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CN114805912A
CN114805912A CN202210363409.4A CN202210363409A CN114805912A CN 114805912 A CN114805912 A CN 114805912A CN 202210363409 A CN202210363409 A CN 202210363409A CN 114805912 A CN114805912 A CN 114805912A
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翁景峥
王辰宇
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Abstract

本发明涉及MOF复合薄膜制备领域，尤其涉及一种用于钾离子电化学传感器的MOF复合多孔敏感膜的制备方法。制备如下：按照K‑MOF3mg，聚合物基体材料30～60mg，o‑NPOE 70～200mg，18‑冠醚5mg，NaTFPB5mg，四氢呋喃5～10ml的比例，称取适量的K‑MOF、聚合物基体材料、O‑NPOE、18‑冠醚和NaTFPB，然后将它们共同溶于四氢呋喃溶液中，磁力搅拌并超声振荡，待其充分溶解后将其倾倒在玻璃片上得到了MOF复合多孔敏感膜。本发明所述用于K+电化学传感器的复合多孔敏感膜对于K+的识别响应时间短，同时本发明的制备方法简单，工艺流程短，有效的提升了生产效率，利于小规模生产。

Description

一种用于K+电化学传感器的MOF复合多孔敏感膜的制备方法
技术领域
本发明涉及MOF复合薄膜制备领域，尤其涉及一种用于钾离子（K+）电化学传感器的MOF复合多孔敏感膜的制备方法。
背景技术
电化学传感器是进行定性和定量的分析和测量，将待测物的化学量转化为电学量进行传感检测的一种传感器装置。
一个典型的电化学传感器的基本元件为：一个工作（或传感）电极、一个对电极，通常还包括一个参比电极。上述电极附于传感器内，衬以电解质。电极位于--块扩散膜的内面上，有多孔供检测物质穿过，但电解质无法渗透。被测物质扩散进入传感器并穿过薄膜到达电极后，将发生电化学反应，或为氧化，或为还原，依物质类型而定。氧化反应使电子通过外电路从工作电极流向对电极;与此相反，还原反应使电子从对电极流向工作电极。上述电子流构成电流，并与气体浓度互成比例。传感器模组及仪器内电路对电流进行检测及放大，最终实现对待测物类别及浓度的测量并输出结果。
MOF，即金属有机框架是一种高比表面积、高孔隙率、易调孔径、易功能化的多孔材料，且MOF中有机配体可以解决兼容性差的问题。含有丰富磺酸根、羧酸根的框架MOF与反应致孔剂之间具有作用，且两者之间有良好的兼容性，因此易制备出均匀致密的复合膜，从而提高膜的性能。此外，MOF的孔道也可以增加膜的传质通道从而提高膜的通量。
本发明利用自然致孔方式制备出高负载量均匀致密且稳定的MOF复合多孔敏感膜，用于测定钾离子的浓度，该方法绿色环保，简单易行，成本相对较低，且有较好的识别效果，具有潜在的应用价值。
发明内容
从解决现有技术中存在的问题为出发点，本发明目的是提供一种适用于K+电化学传感器的MOF复合多孔敏感膜的制备方法。本发明的适用于K+电化学传感器的MOF复合多孔敏感膜表现出优异的检测性能，良好的能斯特响应。
本发明提供了上述一种适用于K+电化学传感器的MOF复合多孔敏感膜的制备方法，包括以下步骤：
为实现本发明的目的采用的制备如下：
1.配比：
K-MOF 3mg
聚合物基体材料 30～60mg
o-NPOE 70～200mg
18-冠醚 5mg
NaTFPB 5mg
四氢呋喃 5～10ml
2.制备：
按比例称取适量的K-MOF、聚合物基体材料、增塑剂O-NPOE、离子载体18-冠醚和离子定域剂 NaTFPB，然后将它们共同溶于重蒸馏后的四氢呋喃溶液中，磁力搅拌并超声振荡30～60分钟，待其充分溶解后，将其倾倒在干净的玻璃片上，在干燥的室温下放置48~72小时待溶剂自然挥发，得到了一张厚度为0.2~0.5mm的富有弹性且半透明的MOF复合多孔敏感膜。
所述的聚合物基体材料是指硅橡胶、聚甲基丙烯酸甲酯（PMMA）、聚丁基丙烯酸酯、羟基或羧基功能化的 PVC（聚氯乙烯）中的一种或任意比例的多种混合。
本发明至少具备以下有益效果：
提出了一种用于K+电化学传感器的二维导电金属有机骨架(K-MOF)复合多孔敏感膜，并对其检测、分析性能进行了展示。本发明制得的适用于K+电化学传感器的MOF复合多孔敏感膜对于K+的识别响应时间短，其在溶剂的浸泡下依旧能保持良好的检测性能，良好的能斯特响应和长期电位稳定性。同时本发明的制备方法简单，工艺流程短，有效的提升了生产效率，利于小规模生产。
本发明在环境监测、即时检测等领域具备了的巨大潜力和市场前景。
附图说明
图1是本发明所述的一种用于K+电化学传感器的MOF复合多孔敏感膜在钾离子浓度为50-2000 mg/L溶液中的电位变化图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
所制备的离子选择性电极在使用前均已经在10-1 M的KCl溶液中活化了 24 h。
实验数据中的电位值都已经按照 Henderson 公式完成了液接电位的校正，溶液活度则根据 Debye-Hückel公式进行了校正。
实施例1
称取3mg K-MOF与30mg PVC、60mg o-NPOE、5mg18-冠醚和5mg NaTFPB，然后将它们共同溶于5ml的四氢呋喃溶液中，磁力搅拌并超声振荡60分钟，待其充分溶解后，将其倾倒在5.5×5.5cm洁净的玻璃片上，在干燥的室温下放置48h后，得到一张厚度为0.4mm的富有弹性且半透明的MOF复合多孔敏感膜。
将本实例构建的MOF复合多孔敏感膜应用于实际样品中检测上，在K+为50-2000mg/L 浓度区间内，其检测的峰电流与浓度的对数线形关系良好，R=0.99784。如附图1所示。
实施例2
称取3mg K-MOF，与50 mg聚丁基丙烯酸酯、100mg o-NPOE、5mg18-冠醚和5mgNaTFPB，然后将它们共同溶于8ml四氢呋喃溶液中，磁力搅拌并超声振荡50分钟，待其充分溶解后，将其倾倒在5.5×5.5cm干净的玻璃片上，在干燥的室温下放置58h后，得到一张厚约为0.4mm的富有弹性且半透明的MOF复合多孔敏感膜。
实施例3
称取3mg K-MOF，与60 mg聚硅氧烷、150mg o-NPOE、5mg18-冠醚和5mg NaTFPB，然后将它们共同溶于10 ml四氢呋喃溶液中，磁力搅拌并超声振荡60分钟，待其充分溶解后，将其倾倒在3.5×3.5cm干净的玻璃片上，在干燥的室温下放置72h后，得到一张度为0.2mm的富有弹性且半透明的MOF复合多孔敏感膜。

Claims (3)

1.一种用于K+电化学传感器的MOF复合多孔敏感膜的制备方法，其特征在于：
1）配比：
K-MOF 3mg
聚合物基体材料 30～60mg
o-NPOE 70～200mg
18-冠醚 5mg
NaTFPB 5mg
四氢呋喃 5～10ml ；
2）制备：
按比例称取适量的K-MOF、聚合物基体材料、增塑剂O-NPOE、离子载体18-冠醚和离子定域剂 NaTFPB，然后将它们共同溶于重蒸馏后的四氢呋喃溶液中，磁力搅拌并超声振荡，待其充分溶解后，将其倾倒在干净的玻璃片上，在干燥的室温下放置48~72小时待溶剂自然挥发，得到了一张厚度为0.2~0.5mm的富有弹性且半透明的MOF复合多孔敏感膜。
2.根据权利要求1所述的一种用于K+电化学传感器的MOF复合多孔敏感膜的制备方法，其特征在于：所述的磁力搅拌并超声振荡的时间为30～60分钟。
3.根据权利要求1所述的一种用于K+电化学传感器的MOF复合多孔敏感膜的制备方法，其特征在于所述的聚合物基体材料是指硅橡胶、聚甲基丙烯酸甲酯、聚丁基丙烯酸酯、羟基或羧基功能化的聚氯乙烯中的一种或任意比例的多种混合。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109187688A (zh) * 2018-12-05 2019-01-11 中国科学院烟台海岸带研究所 一种光控的聚合物敏感膜电化学检测方法及其装置
CN111044587A (zh) * 2019-11-25 2020-04-21 西安医学院 电化学传感器用2d卟啉mof纳米材料及其制备方法
CN113462051A (zh) * 2021-05-21 2021-10-01 浙江大学 一种超支化聚乙烯基多孔液体及其制备方法
CN113671005A (zh) * 2021-07-01 2021-11-19 广州大学 一种基于mof的铜离子选择性电极及其制备方法与应用
WO2022018697A1 (en) * 2020-07-24 2022-01-27 Monash University Crown ether metal organic framework compositions and methods

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109187688A (zh) * 2018-12-05 2019-01-11 中国科学院烟台海岸带研究所 一种光控的聚合物敏感膜电化学检测方法及其装置
CN111044587A (zh) * 2019-11-25 2020-04-21 西安医学院 电化学传感器用2d卟啉mof纳米材料及其制备方法
WO2022018697A1 (en) * 2020-07-24 2022-01-27 Monash University Crown ether metal organic framework compositions and methods
CN113462051A (zh) * 2021-05-21 2021-10-01 浙江大学 一种超支化聚乙烯基多孔液体及其制备方法
CN113671005A (zh) * 2021-07-01 2021-11-19 广州大学 一种基于mof的铜离子选择性电极及其制备方法与应用

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