CN105536745B - 一种金属有机骨架固相微萃取纤维及其制备方法 - Google Patents

一种金属有机骨架固相微萃取纤维及其制备方法 Download PDF

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CN105536745B
CN105536745B CN201510937398.6A CN201510937398A CN105536745B CN 105536745 B CN105536745 B CN 105536745B CN 201510937398 A CN201510937398 A CN 201510937398A CN 105536745 B CN105536745 B CN 105536745B
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牛佳佳
范黎
贺琛
叶长文
陈宸
李栋
张勍
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Zhengzhou Tobacco Research Institute of CNTC
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Abstract

本发明公开了一种金属有机骨架固相微萃取纤维及其制备方法，该固相微萃取纤维选用不锈钢丝作为载体，表面采用氢氟酸腐蚀粗糙化处理。以Zn(NO3)2•6H2O、2,2‑双(4‑羧基苯基)六氟丙烷和乙酸钠为原料制备氟孔道金属有机骨架材料（简称Zn‑FMOF）；以芳香二胺和芳香二酐为原料冰浴下混合制得聚酰胺酸溶液，后加入Zn‑FMOF粉末超声分散，将处理过的不锈钢丝***混合溶液浸渍涂覆，后置于烘箱高温下固化，重复该过程5～10次得到固相微萃取纤维。该纤维具有稳定性好、吸附性能优异、耐湿性好以及使用寿命长等特点，可用于食品、环境、卷烟烟气等实际样品中痕量组分的分析。

Description

一种金属有机骨架固相微萃取纤维及其制备方法
技术领域
本发明涉及固相微萃取纤维制备技术，具体地说是一种金属有机骨架固相微萃取纤维及其制备方法，属于分析化学领域。
背景技术
固相微萃取（SPME）是一种新兴的样品前处理技术，它是利用涂覆在纤维上的涂层材料将样品中的目标吸附、分离和富集。由于SPME技术是集萃取、浓缩、解吸和进样于一体的样品预处理技术，具有使用方便、快捷、无需有机溶剂、灵敏、价廉等优点，已被广泛用于样品预处理。
SPME技术的核心在于纤维上的涂层材料，目前商品化的涂层有聚二甲基硅氧烷（PDMS）、聚丙烯酸（PA）、聚乙二醇（CW）和碳分子筛（CAR）等不同厚度的单一、混合或共聚物涂层。对于特定的样品，选用合适的涂层非常重要。目前商品化的涂层种类有限，而且价格昂贵，适用温度较低，所以制备适用范围广、廉价的涂层显得非常重要。另一方面，现有技术制备的萃取纤维难以在超过300℃的条件下使用，且对于目标物的吸附能力有待进一步提高。
金属-有机骨架（Metal-Organic Frameworks, MOFs）材料是一类由金属与有机配体通过配位键构筑的多孔材料。结构的可调控性是它的重要特点之一，通过选择不同的金属中心和桥连配体可有效的调节MOFs 的骨架结构，孔道形状、尺寸以及孔道内表面化学环境等。多样可调的孔道结构，良好的吸附性能，较好的热稳定性使其成为SPME 涂层的理想候选。石英是制备SPME纤维的常用载体，但机械性能差，操作过程极易出现石英载体的断裂，严重影响了萃取头的使用寿命，金属丝载体如不锈钢丝可以解决这一问题。目前利用金属丝载体制备MOFs 涂层的SPME 纤维大多采用原位生长、物理沉降的方法，但这种方法制备的纤维在反复的萃取和高温解吸过程中容易脱落，寿命较短，难以保证萃取效率和重现性。综上所述，发展一种合适的制备方法将高性能的MOFs材料牢固地结合在金属载体，制备出富集能力强、稳定性好、使用寿命长的新型MOFs涂层SPME纤维是非常必要的。
发明内容：
本发明目的旨在提供一种富集效率高、稳定性好、使用寿命长的新型SPME纤维。
本发明的目的是通过以下技术方案来实现的：
一种金属有机骨架固相微萃取纤维，包括金属载体和附着在其表面的涂层，其中：金属载体为长度5-9cm的不锈钢丝，不锈钢丝的一端（约2-3cm）涂覆有涂层材料，该涂层材料为聚酰亚胺（简称PI）与Zn-FMOF所形成的复合材料（简称PI/Zn-FMOF），也就是聚酰亚胺与氟孔道金属有机骨架所形成的复合材料。具体步骤如下：
1）Zn-FMOF的制备
Zn(NO3)2•6H2O、2,2-双(4-羧基苯基)六氟丙烷和乙酸钠按照1:2.6:1的摩尔比加入到水和异丙醇（9:1）的混合溶液中，室温下搅拌均匀，溶液转移至内衬为聚四氟乙烯的不锈钢反应釜，180℃下反应24h，得到白色针状晶体，过滤用水洗3次，80℃下干燥后研磨成细微颗粒；
2）聚酰胺酸溶液的制备
取2 mmol的芳香二胺搅拌条件下加入到盛有10～20 mL无水二甲基甲酰胺的锥形瓶中，待完全溶解后在冰浴条件下加入等摩尔比的芳香二酐，得到聚酰胺酸黄色溶液；
3）不锈钢丝处理
依次用丙酮、甲醇和蒸馏水超声处理不锈钢丝，后在空气中干燥后，将钢丝一头（约3cm）置于氢氟酸溶液中5～10 min，后用蒸馏水冲洗，室温下干燥待用；
4）固相微萃取纤维制备
取制备的Zn-FMOF粉末0.3～1 g，置于上述聚酰胺酸溶液后超声分散5～10 min；将处理过的不锈钢丝***混合溶液浸渍涂覆，后置于烘箱180～230℃下固化20～30 min，重复该浸渍涂覆及烘箱固化过程5～10次得到固相微萃取纤维。
所述芳香二胺为对苯二胺、3, 3'-二胺基二苯酮、4,4'-二氨基二苯醚；所述芳香二酐为均苯四甲酸酐、3, 3', 4, 4'-二苯甲酮四羧酸二酐。
本发明提供了一种简单、快速、高效的SPME纤维制备方法，具有如下优势：1）采用PI与Zn-FMOF复合的策略，一步制备PI/Zn-FMOF复合材料，同时完成复合材料在钢丝表面成膜；2）利用Zn-FMOF高的比表面积、规整的孔道等结构特征，从而使PI/Zn-FMOF复合材料涂层具备对有机小分子良好的富集性能；3）PI、Zn-FMOF两种材料均具有较好的高温稳定性、水和空气稳定性，因此基于不锈钢丝所制备的PI/Zn-FMOF复合材料SPME纤维具备高的稳定性和使用寿命，同时可以应用于高湿性样品的检测中。
附图说明
图1：本发明实例1所制备SPME纤维扫描电镜图（a为表面图，b为截面图）；
图2：本发明实例2所制备SPME纤维扫描电镜图。
具体实施方式
本发明以下结合实例做进一步描述，但并不是限制本发明。
实施例1：
1. Zn-FMOF的制备
根据权利要求书中限定的摩尔比，称取0.36 g Zn(NO3)2•6H2O，0.47 g 2,2-双(4-羧基苯基)六氟丙烷和0.1 g乙酸钠加入到54 mL水和6 mL异丙醇的混合溶剂中，室温下搅拌均匀。溶液转移至内衬为聚四氟乙烯的不锈钢反应釜中，180℃下反应24h，得到白色针状晶体，过滤用水洗3次，80℃下干燥后研磨成细微颗粒。
2. 聚酰胺酸溶液的制备
取2 mmol 4,4'-二氨基二苯醚搅拌条件下加入到盛有10 mL无水二甲基甲酰胺的锥形瓶中，待完全溶解后在冰浴条件下加入2 mmol均苯四甲酸酐，得到聚酰胺酸黄色溶液。
3. 不锈钢丝处理
依次用丙酮、甲醇和蒸馏水超声处理不锈钢丝，后在空气中干燥后，将钢丝一头（约3cm）置于氢氟酸溶液中5 min，后用蒸馏水冲洗，室温下干燥待用。
4. SPME纤维制备
取制备的Zn-FMOF粉末0.5 g，置于聚酰胺酸溶液后超声分散5 min。将处理过的不锈钢丝***混合溶液浸渍涂覆，后置于烘箱200℃下固化30 min，重复该过程6次得到SPME纤维。
实施例2：
1. Zn-FMOF的制备
根据权利要求书中限定的摩尔比，称取0.36 g Zn(NO3)2•6H2O，0.47 g 2,2-双(4-羧基苯基)六氟丙烷和0.1 g乙酸钠加入到54 mL水和6 mL异丙醇的混合溶剂中，室温下搅拌均匀。溶液转移至四氟乙烯的不锈钢反应釜中，180℃下反应24h，得到白色针状晶体，过滤用水洗3次，80℃下干燥后研磨成细微颗粒。
2. 聚酰胺酸溶液的制备
取2 mmol对苯二胺搅拌条件下加入到盛有15 mL无水二甲基甲酰胺的锥形瓶中，待完全溶解后在冰浴条件下加入2 mmol 3, 3', 4, 4'-二苯甲酮四羧酸二酐，得到聚酰胺酸黄色溶液。
3. 不锈钢丝处理
依次用丙酮、甲醇和蒸馏水超声处理不锈钢丝，后在空气中干燥后，将钢丝一头（约3cm）置于氢氟酸溶液中8 min，后用蒸馏水冲洗，室温下干燥待用。
4. SPME纤维制备
取制备的Zn-FMOF粉末0.8 g，置于聚酰胺酸溶液后超声分散10 min。将处理过的不锈钢丝***混合溶液浸渍涂覆，后置于烘箱220℃下固化25 min，重复该过程5次得到SPME纤维。

Claims (2)

1.一种金属有机骨架固相微萃取纤维，包括金属载体和附着在其表面的涂层，其特征在于：金属载体为长度5-9cm的不锈钢丝，不锈钢丝的一端涂覆有涂层材料，该涂层材料为聚酰亚胺PI与Zn-FMOF所形成的复合材料，简称PI/Zn-FMOF；所述金属有机骨架固相微萃取纤维的制备方法如下：
1）Zn-FMOF的制备
Zn(NO3)2•6H2O、2,2-双(4-羧基苯基)六氟丙烷和乙酸钠按照1:2.6:1的摩尔比加入到水和异丙醇体积比为9:1的混合溶液中，室温下搅拌均匀，溶液转移至内衬为聚四氟乙烯的不锈钢反应釜，180℃下反应24h，得到白色针状晶体，过滤用水洗3次，80℃下干燥后研磨成细微颗粒；
2）聚酰胺酸溶液的制备
取2 mmol的芳香二胺搅拌条件下加入到盛有10～20 mL无水二甲基甲酰胺的锥形瓶中，待完全溶解后在冰浴条件下加入等摩尔的芳香二酐，得到聚酰胺酸黄色溶液；
3）不锈钢丝处理
依次用丙酮、甲醇和蒸馏水超声处理不锈钢丝，后在空气中干燥后，将钢丝一头置于氢氟酸溶液中5～10 min，后用蒸馏水冲洗，室温下干燥待用；
4）固相微萃取纤维制备
取制备的Zn-FMOF粉末0.3～1 g，置于上述聚酰胺酸溶液后超声分散5～10 min；将处理过的不锈钢丝***混合溶液浸渍涂覆，后置于烘箱180～230℃下固化20～30 min，重复该浸渍涂覆及烘箱固化过程5～10次得到固相微萃取纤维。
2.如权利要求1所述的金属有机骨架固相微萃取纤维，其特征在于：在步骤2）中，所述芳香二胺为对苯二胺、3, 3'-二胺基二苯酮、4,4'-二氨基二苯醚；所述芳香二酐为均苯四甲酸酐、3, 3', 4, 4'-二苯甲酮四羧酸二酐。
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