CN108619917B - 一种硫化氢传感用金属-有机框架基混合基质膜及其制备方法 - Google Patents
一种硫化氢传感用金属-有机框架基混合基质膜及其制备方法 Download PDFInfo
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Abstract
本发明公开一种硫化氢传感用金属‑有机框架基混合基质膜及其制备方法,属于有机/无机杂化膜材料制备技术及其应用方向。该方法是在高分子聚合物基质材料中加入金属‑有机框架功能体,制备出具有三维网状结构的混合基质膜,其按质量百分比计组分为:聚合物5~25%;金属‑有机框架颗粒2~30%;溶剂45~90%,各组分之和为100%,混合基质膜制备方法包括以下工艺:1.铸膜液的制备;2.制膜;3.存储。所制得的传感功能膜可用于工业废水中硫化氢的传感,该柔性传感功能膜具有高的选择性和灵敏度。此外,合成该混合基质膜的原料廉价易得,制作膜材料的过程简单易行,可放大进行大规模的生产,应用于工业废水中硫化氢的传感。
Description
技术领域
本发明属于有机/无机杂化膜材料制备技术及其应用方向,涉及一种硫化氢传感用金属-有机框架基混合基质膜及其制备方法。
背景技术
金属-有机框架(Metal-organic Framework,MOFs)材料是一类由有机配体与金属中心经过自组装形成的具有可调节孔径的材料。其源于配位化学及晶体学理论而发展,微观形态呈规则的几何状,有均一的孔道及孔径。由于MOFs具有合成方法灵活、比表面积大、种类和性质多样、孔和晶体尺寸可调和热稳定性好等优点,从而有望成为新一代膜材料。根据制膜工艺的不同,MOF膜材料大致可以分为MOF晶体膜和以MOF为添加剂的混合基质膜。通常地,MOF晶体膜是一类在氧化铝或二氧化钛等载体上连续生长MOF的多孔膜。因此,这类MOF膜具有较高的渗透通量和适中的选择性。相比较而言,以MOF晶体为分散相和以聚合物为连续相的混合基质膜则表现出低渗透通量和高选择性的特点。近几年MOF膜的研究报道持续增长,但主要集中在MOF膜在分离方面的应用。本发明根据MOFs和混合基质膜的特性设计合成具有传感功能的MOF基混合基质膜。MOF基混合基质传感膜与传统的粉体MOFs传感器相比具有较高的灵敏度,与纯MOFs膜相比具有较好的柔韧性,因此该传感功能膜具有广阔的应用前景。
发明内容
针对现有技术的不足,本发明提出一种硫化氢传感用金属-有机框架基混合基质膜及其制备方法,将金属-有机框架材料与多孔膜技术相结合,制备用于硫化氢传感的杂化膜。
本发明解决所述技术问题的技术方案是:设计了一种金属-有机框架基混合基质膜,其铸膜液的质量百分比配方为:
聚合物 5~25%;
金属-有机框架颗粒 2~30%;
溶剂 45~90%;
上述各组分之和为100%;
所述的聚合物为聚酰亚胺、聚砜、聚偏氟乙烯中的至少一种;
所述的金属-有机框架颗粒为Al-MIL-53-NO2;
所述的金属-有机框架颗粒的粒径优选为20~200nm。
所述的溶剂为N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、甲醇、乙醇、三氯甲烷、丙酮或四氢呋喃中的至少一种。
上述的金属-有机框架基混合基质膜的制备方法,其特征在于,包括如下步骤:
(1)铸膜液的制备:按照上述金属-有机框架基混合基质膜配方的质量百分比要求,首先将所述的聚合物和溶剂混合,在20~80℃下搅拌12~36小时,然后将金属-有机框架颗粒加入到上述混合溶液中,在20~80℃下再搅拌12~36小时,制得混合均匀的铸膜液;
(2)制膜:在20~90℃下,将制得的铸膜液在平面板上刮涂成平板膜,再将其置于温度20~90℃的凝固浴中浸泡0.5~24小时凝固成形,即可制得金属-有机框架基混合基质膜;
(3)存储:将功能膜浸润在去离子水中。
本发明制得的金属-有机框架混合基质传感膜具有表面开孔结构,无机颗粒分布在三维膜孔道中,这些孔道为金属-有机框架颗粒与待检测硫化氢的充分接触提供了保障。本发明制备出的金属-有机框架混合基质传感膜与传统的金属-有机框架粉体传感材料相比有很大优势,粉体材料易于团聚,在待测溶液中很难分散均匀,而膜材料就可以通过搅拌使金属有机框架材料在聚合物中分散均匀,更利于硫化氢与金属有机框架的接触;实际应用中粉体材料是没有办法应用的,必须要把粉体材料制成某种形状才可以应用,而应用膜材料就不存在这样的问题,本发明制备的是柔性膜,可以根据需要制备成不同的形状;该膜的灵敏度要比传统粉体高出至少两个数量级。与纯金属有机框架膜材料相比,该金属-有机框架混合基质传感膜也有很多优势,纯金属有机框架膜材料制备条件苛刻,必须在基底上生长,不能大面积生长,无柔韧性,实际应用较为困难,而金属-有机框架混合基质传感膜制造方法具有工艺速度快、方法简单、原料来源广等特点,在玻璃板上刮涂之后很容易揭下来,具有较好的柔韧性,能够大面积制备。
附图说明
图1为本发明实施例1合成的Al-MIL-53-NO2基混合基质膜的上表面。
图2为本发明实施例2合成的Al-MIL-53-NO2基混合基质膜的截面。
图3为本发明实施例1合成的Al-MIL-53-NO2基混合基质膜对硫化氢的选择性。
具体实施方式
下面将结合实施例进一步阐明本发明的内容,但这些实例并不限制本发明的保护范围,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。
实施例1
首先将150mg聚偏氟乙烯溶于1.9g N,N-二甲基甲酰胺,在25℃下搅拌24小时,然后将350mg金属-有机框架颗粒Al-MIL-53-NO2加入到上述混合溶液中,在25℃下再搅拌24小时,制得混合均匀的铸膜液;在25℃下,取适量的铸膜液用刮刀刮涂在干净平整的玻璃板表面,再将其置于温度25℃的凝固浴中浸泡0.5小时凝固成形,即可制得Al-MIL-53-NO2基混合基质膜。
实施过程:取4cm2所制备的Al-MIL-53-NO2基混合基质膜将其固定在250mL真空抽滤装置的砂芯漏斗上,在真空泵工作中下使200mL 1mM分别含有阴离子(HS-,NO3 -,NO2 -,N3 -,Cl-,Br-,I-,CO3 2-,HCO3 -,H2PO4 -)和阳离子(Al3+,Cu2+,Zn2+,Pb2+)得水溶液通过Al-MIL-53-NO2基混合基质膜,将该膜拿去测光谱,发现只有硫化氢能够使该传感膜发光增强。
实施效果:Al-MIL-53-NO2基混合基质膜对硫化氢具有较高的选择性和灵敏度(检测限92.31nM)。
实施例2
首先将160mg聚砜溶于2g三氯甲烷,在30℃下搅拌24小时,然后将370mg金属-有机框架颗粒Al-MIL-53-NO2加入到上述混合溶液中,在30℃下再搅拌24小时,制得混合均匀的铸膜液;在25℃下,取适量的铸膜液用刮刀刮涂在干净平整的玻璃板表面,再将其置于温度25℃的凝固浴中浸泡1.5小时凝固成形,即可制得Al-MIL-53-NO2基混合基质膜。
实施效果:Al-MIL-53-NO2基混合基质膜对硫化氢具有较高的选择性和灵敏度(检测限115.08nM)。
Claims (4)
1.一种硫化氢传感用金属-有机框架基混合基质膜,其特征在于,其铸膜液的质量百分比配方为:
聚合物 5 ~ 25%;
金属-有机框架颗粒 2 ~ 30%;
溶剂 45 ~ 90%;
上述各组分之和为100%;
所述的聚合物为聚酰亚胺、聚砜、聚偏氟乙烯中的至少一种;
所述的金属-有机框架颗粒为Al-MIL-53-NO2;
所述的溶剂为N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、甲醇、乙醇、三氯甲烷、丙酮或四氢呋喃中的至少一种;
其制备方法包括如下步骤:
(1) 铸膜液的制备:按照上述金属-有机框架基混合基质膜配方的质量百分比要求,首先将所述的聚合物和溶剂混合,在20 ~ 80℃下搅拌12 ~ 36 小时,然后将金属-有机框架颗粒加入到上述混合溶液中,在20 ~ 80℃下再搅拌12 ~ 36 小时,制得混合均匀的铸膜液;
(2) 制膜:在20 ~ 90℃下,将制得的铸膜液在平面板上刮涂成平板膜,再将其置于温度20 ~ 90℃的凝固浴中浸泡0.5 ~ 24 小时凝固成形,即可制得金属-有机框架基混合基质膜;
(3) 存储:将功能膜浸润在去离子水中。
2. 根据权利要求1 所述的金属-有机框架基混合基质膜,其特征在于,所述的金属-有机框架颗粒的粒径分布在20 ~ 200 nm。
3. 根据权利要求1 所述的金属-有机框架基混合基质膜,其特征在于,所述的平面板包括平面的玻璃板或不锈钢板;所述的刮涂方式采用刮刀或刮棒手工刮制。
4.根据权利要求1所述的金属-有机框架基混合基质膜,其特征在于,所述的凝固浴为去离子水、甲醇、丙酮中至少一种。
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