CN110453501A - 一种基于pani-pani纳米纤维复合气敏材料的制备方法 - Google Patents

一种基于pani-pani纳米纤维复合气敏材料的制备方法 Download PDF

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CN110453501A
CN110453501A CN201910761490.XA CN201910761490A CN110453501A CN 110453501 A CN110453501 A CN 110453501A CN 201910761490 A CN201910761490 A CN 201910761490A CN 110453501 A CN110453501 A CN 110453501A
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Abstract

本发明涉及复合气敏材料制备技术领域，且公开了一种基于PANI‑PANI纳米纤维复合气敏材料的制备方法，包括以下步骤：步骤一，采用静电纺丝法制备PANI纳米纤维；步骤二，采用溶液原位聚合法在PANI纳米纤维表面聚合生成具有离域π电子共轭体系的导电聚合物聚苯胺PANI。本发明解决了目前现有的基于静电纺丝法所制备的PANI纳米纤维在运用到气体传感器时，一直存在电极基底与PANI纳米纤维气敏材料的接触电阻较大，难以测定气体的技术问题。

Description

一种基于PANI-PANI纳米纤维复合气敏材料的制备方法
技术领域
本发明涉及复合气敏材料制备技术领域，具体为一种基于PANI-PANI纳米纤维复合气敏材料的制备方法。
背景技术
聚苯胺(PANI)导电聚合物是具有离域π电子共轭体系的聚合物，当其掺杂后，电子或者空穴注入到单双键交替排列形成的超轨道中，使其具有导电性，并且可以通过调节掺杂程度来调节导电率大小；而当掺杂后的PANI导电聚合物与气体分子接触后，吸附的气体分子可以从其主链上得到或者失去电子，使掺杂状态发生改变而影响导电率大小，导电性能发生的改变通过转换器件将其转换为可输出的电信号，即可实现检测气体的技术目的。
PANI可以在存有氧化剂的质子酸溶液中通过苯胺制备，也可以恒电压下或者循环电势下的质子酸溶液或者有机溶剂中合成，前者一般称为化学法，后者为电化学法。典型的PANI制备在盐酸溶液中由过硫酸铵(APS)作为氧化剂引发苯胺聚合，但是制得的PANI难溶于普通溶剂，不易成膜，而且熔融加工时也不稳定，制约了其在气体传感器方面的应用。
而基于静电纺丝法得到的PANI纳米纤维和传统的薄膜或者多孔材料相比，具有更大的比表面积体积比，因此有利于气体的吸附和脱吸附，可以提高气体传感器的响应特性，如响应时间、灵敏度和稳定性等。但是基于静电纺丝法所制备的PANI纳米纤维在运用到气体传感器时，一直存在传感器的基底和PANI纳米纤维的接触电阻较大，导致难以测定的问题。
发明内容
(一)解决的技术问题
针对现有技术的不足，本发明提供了一种基于PANI-PANI纳米纤维复合气敏材料的制备方法，解决了目前现有的基于静电纺丝法所制备的PANI纳米纤维在运用到气体传感器时，一直存在电极基底与PANI纳米纤维气敏材料的接触电阻较大，难以测定气体的技术问题。
(二)技术方案
为实现上述目的，本发明提供如下技术方案：
一种基于PANI-PANI纳米纤维复合气敏材料的制备方法，包括以下步骤：
步骤一：采用静电纺丝法制备PANI纳米纤维；
步骤二：采用溶液原位聚合法在PANI纳米纤维表面聚合生成具有离域π电子共轭体系的导电聚合物聚苯胺PANI。
优选的，所述步骤一中，静电纺丝以铜板为收集板，在收集板上沉积静电纺丝制得PANI纳米纤维。
优选的，所述步骤一中，静电纺丝电压为20KV、溶液流速为0.2～0.6ML/h。
优选的，所述掺杂酸包括甲苯磺酸TSA、磺基水杨酸SSA、盐酸HCl中的一种或几种。
(三)有益的技术效果
与现有技术相比，本发明具备以下有益的技术效果：
本发明先采用静电纺丝法制备PANI纳米纤维，再采用溶液原位聚合法在PANI纳米纤维表面生成具有离域π电子共轭体系的导电聚合物聚苯胺PANI，PANI纳米纤维表面的聚苯胺PANI有效地降低了电极基底与PANI纳米纤维气敏材料的接触电阻；
经测试，本发明的PANI-PANI纳米纤维复合气敏材料对100ppmNH3气的响应时间为33～37s、响应灵敏度为80～83％，与对比例中的PANI纳米纤维气敏材料对100ppmNH3气的响应时间为104s、响应灵敏度为32％相比，取得了显著提高PANI纳米纤维在运用到气体传感器时的响应性能的技术效果。
具体实施方式
实施例一：
基于PANI-PANI纳米纤维复合气敏材料的制备方法，包括以下步骤：
步骤一：将装有0.2g/mL聚苯胺(PANI)的N,N-二甲基甲酰胺(DMF)溶液的注射器固定在注射泵上，注射器注射针头与高压直流电源的阳极相连，以铜板为收集板、并接地作为阴极，将尺寸为18mm×18mm的盖玻片置于铜板上，在其上沉积静电纺丝制得PANI纳米纤维；
其中，静电纺丝电压为20KV、溶液流速为0.2ML/h、针头和收集板之间的距离为15cm；
步骤二：在50mL去离子水中加入0.227mL苯胺(0.05M)，0.28g过硫酸铵(0.025M)和0.1mL由对甲苯磺酸TSA(0.05M)、磺基水杨酸SSA(0.05M)、盐酸HCl(0.05M)组成的掺杂酸，搅拌10min；
之后，将步骤一制备的沉积有PANI纳米纤维无纺布的盖玻片放置其中，PANI薄膜悬浮在液面，在室温下聚苯胺将同时在溶液和纤维表面进行聚合，聚合40min后，将表面沉积有PANI的PANI无纺布薄膜取出，并用由对甲苯磺酸TSA(0.05M)、磺基水杨酸SSA(0.05M)、盐酸HCl(0.05M)组成的掺杂酸溶液洗涤，除去电极表面聚苯胺颗粒和残余的试剂，得到PANI-PANI纳米纤维复合气敏材料。
实施例二：
基于PANI-PANI纳米纤维复合气敏材料的制备方法，包括以下步骤：
步骤一：将装有0.4g/mL聚苯胺(PANI)的N,N-二甲基甲酰胺(DMF)溶液的注射器固定在注射泵上，注射器注射针头与高压直流电源的阳极相连，以铜板为收集板、并接地作为阴极，将尺寸为18mm×18mm的盖玻片置于铜板上，在其上沉积静电纺丝制得PANI纳米纤维；
其中，静电纺丝电压为20KV、溶液流速为0.4ML/h、针头和收集板之间的距离为15cm；
步骤二：在50mL去离子水中加入0.454mL苯胺(0.05M)，0.28g过硫酸铵(0.05M)和0.1mL由对甲苯磺酸TSA(0.5M)、磺基水杨酸SSA(0.5M)、盐酸HCl(0.5M)组成的掺杂酸，搅拌20min；
之后，将步骤一制备的沉积有PANI纳米纤维无纺布的盖玻片放置其中，PANI薄膜悬浮在液面，在室温下聚苯胺将同时在溶液和纤维表面进行聚合，聚合80min后，将表面沉积有PANI的PANI无纺布薄膜取出，并用由对甲苯磺酸TSA(0.5M)、磺基水杨酸SSA(0.5M)、盐酸HCl(0.5M)组成的掺杂酸溶液洗涤，除去电极表面聚苯胺颗粒和残余的试剂，得到PANI-PANI纳米纤维复合气敏材料。
实施例三：
基于PANI-PANI纳米纤维复合气敏材料的制备方法，包括以下步骤：
步骤一：将装有0.8g/mL聚苯胺(PANI)的N,N-二甲基甲酰胺(DMF)溶液的注射器固定在注射泵上，注射器注射针头与高压直流电源的阳极相连，以铜板为收集板、并接地作为阴极，将尺寸为18mm×18mm的盖玻片置于铜板上，在其上沉积静电纺丝制得PANI纳米纤维；
其中，静电纺丝电压为20KV、溶液流速为0.6ML/h、针头和收集板之间的距离为15cm；
步骤二：在50mL去离子水中加入0.227mL苯胺(0.05M)，0.28g过硫酸铵(0.25M)和0.1mL由对甲苯磺酸TSA(0.1M)、磺基水杨酸SSA(0.1M)、盐酸HCl(0.1M)组成的掺杂酸，搅拌40min；
之后，将步骤一制备的沉积有PANI纳米纤维无纺布的盖玻片放置其中，PANI薄膜悬浮在液面，在室温下聚苯胺将同时在溶液和纤维表面进行聚合，聚合40min后，将表面沉积有PANI的PANI无纺布薄膜取出，并用由对甲苯磺酸TSA(0.1M)、磺基水杨酸SSA(0.1M)、盐酸HCl(0.1M)组成的掺杂酸溶液洗涤，除去电极表面聚苯胺颗粒和残余的试剂，得到PANI-PANI纳米纤维复合气敏材料。
对比例：
基于PANI纳米纤维气敏材料的制备方法，包括以下步骤：
步骤一：将装有0.8g/mL聚苯胺(PANI)的N,N-二甲基甲酰胺(DMF)溶液的注射器固定在注射泵上，注射器注射针头与高压直流电源的阳极相连，以铜板为收集板、并接地作为阴极，将尺寸为18mm×18mm的盖玻片置于铜板上，在其上沉积静电纺丝制得PANI纳米纤维。
性能测试：
将实施例中制备的PANI-PANI纳米纤维复合气敏材料与对比例中制备的PANI纳米纤维气敏材料制成气敏元件，对气敏元件的气敏性能进行测试，结果如下表1。
表1
产品编号 对100ppm NH<sub>3</sub>的响应时间(s) 对100ppm NH<sub>3</sub>的响应灵敏度(％)
实施例一 37 81
实施例二 35 83
实施例三 33 80
对比例 104 32

Claims (4)

1.一种基于PANI-PANI纳米纤维复合气敏材料的制备方法，其特征在于，包括以下步骤：
步骤一：采用静电纺丝法制备PANI纳米纤维；
步骤二：采用溶液原位聚合法在PANI纳米纤维表面聚合生成具有离域π电子共轭体系的导电聚合物聚苯胺PANI。
2.根据权利要求1所述的制备方法，其特征在于，所述步骤一中，静电纺丝以铜板为收集板，在收集板上沉积静电纺丝制得PANI纳米纤维。
3.根据权利要求1所述的制备方法，其特征在于，所述步骤一中，静电纺丝电压为20KV、溶液流速为0.2～0.6ML/h。
4.根据权利要求1所述的制备方法，其特征在于，所述掺杂酸包括甲苯磺酸TSA、磺基水杨酸SSA、盐酸HCl中的一种或几种。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101226161A (zh) * 2008-01-31 2008-07-23 浙江大学 聚甲基丙烯酸甲酯/聚苯胺纳米纤维复合电阻型薄膜气敏元件及其制作方法
CN102561042A (zh) * 2012-01-10 2012-07-11 青岛大学 一种枝状纳米结构聚苯胺气敏传感器的制备方法
CN105802950A (zh) * 2016-05-24 2016-07-27 天津工业大学 一种串珠状静电纺纳米纤维固定化酵母菌及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101226161A (zh) * 2008-01-31 2008-07-23 浙江大学 聚甲基丙烯酸甲酯/聚苯胺纳米纤维复合电阻型薄膜气敏元件及其制作方法
CN102561042A (zh) * 2012-01-10 2012-07-11 青岛大学 一种枝状纳米结构聚苯胺气敏传感器的制备方法
CN105802950A (zh) * 2016-05-24 2016-07-27 天津工业大学 一种串珠状静电纺纳米纤维固定化酵母菌及其制备方法

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Application publication date: 20191115