化工进展 ›› 2020, Vol. 39 ›› Issue (9): 3757-3765.DOI: 10.16085/j.issn.1000-6613.2019-1886

• 精细化工 • 上一篇    下一篇

三硝基甲苯分子印迹电化学传感器的制备和应用

王成(), 郭建良, 饶国宁()   

  1. 南京理工大学化工学院,江苏 南京 210094
  • 出版日期:2020-09-05 发布日期:2020-09-11
  • 通讯作者: 饶国宁
  • 作者简介:王成(1996—),男,硕士研究生,研究方向为危险违禁物检测。E-mail:1825871793@qq.com

Preparation and application of TNT electrochemical sensor based on molecularly imprinted polymer

Cheng WANG(), Jianliang GUO, Guoning RAO()   

  1. School of Chemical Engineering,Nanjing University of Science and Technology, Nanjing 210094, Jiangsu, China
  • Online:2020-09-05 Published:2020-09-11
  • Contact: Guoning RAO

摘要:

以三硝基甲苯(TNT)为模板分子,甲基丙烯酸(MAA)为功能单体,采用乳液聚合法制备TNT的分子印迹聚合物(MIPs)。将制备的MIPs分散在溶剂中,通过表面涂覆法制备出检测TNT的分子印迹电化学传感器。紫外光谱表明TNT与MAA之间存在相互作用力,有助于形成结构稳定、亲和性强的MIPs。利用扫描电镜观测不同制备条件下印迹聚合物的表观形貌,发现溶剂用量为30mL、乳化剂用量为12mg时制备的聚合物形貌较优异。吸附实验表明MIPs对TNT的吸附量随着TNT初始浓度的增加而增加,140min后达到最大吸附量的95%。MIPs对TNT的分离常数远大于RDX和DNT,对RDX和DNT的选择性系数均达到4.4以上,说明MIPs对TNT有较好的选择性吸附能力。铁氰化钾探针实验和对TNT的响应曲线验证了电化学传感器的成功制备,该传感器富集3min就达到了最大电流值的94%,5min内达到吸附平衡。TNT浓度在0.1~5mg/mL的范围内与峰电流有良好的线性关系,检出限为0.06mg/mL。MIPs传感器对TNT的电流响应分别为DNT和RDX的3.13倍、3.27倍,说明其对TNT分子具有很强的特异性识别能力。

关键词: 分子印迹, 乳液聚合, 三硝基甲苯, 电化学传感器

Abstract:

The molecularly imprinted polymers(MIPs)of 2,4,6-trinitrotoluene(TNT)were prepared by emulsion polymerization method using TNT as the template molecule and methacrylic acid(MAA)as the functional monomer. The MIPs were dispersed in the solvent and MAA as the functional monomer. The MIPs were dispersed in the solvent and the molecularly imprinted electrochemical sensor for detecting TNT was prepared by surface coating method. The ultraviolet spectrum showed that there was an interaction between TNT and MAA, which helped to form MIPs with stable structure and strong affinity. The morphologies of the polymers were observed by scanning electron microscopy(SEM). It was found that the polymers prepared with 30mL solvent and 12mg emulsifier were better than others. Adsorption experiments showed that the adsorption capacity of MIPs on TNT increased with the increase of the initial concentration of TNT, reaching 95% of the maximum adsorption capacity after 140 min. The separation constants of MIPs for TNT were much higher than RDX and DNT, and the selectivity coefficients of RDX and DNT both reached 4.4 or above, indicating that MIPs had a good selective adsorption capacity for TNT. The successful preparation of electrochemical sensor was verified by potassium ferricyanide probe experiment and TNT response curve. The concentration of the sensor reached 94% of the maximum current value within 3min and reached adsorption equilibrium within 5min. TNT concentration had a good linear relationship with peak current within the range of 0.1—5mg/mL and the detection limit was 0.06mg/mL. The current response of MIPs sensor to TNT was 3.13 times and 3.27 times that of DNT and RDX respectively, showing that it had a strong specific recognition ability to TNT molecule.

Key words: molecular imprinting, emulsion polymerization, TNT, electrochemical sensor

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