CN111024789A - 一种高灵敏度检测2,4-二氯酚的电化学传感器及其检测方法 - Google Patents
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Abstract
本发明公开了一种高灵敏度检测2，4‑二氯酚的电化学传感器及其制备方法，属于电化学传感器领域。上述所述电化学传感器的电极表面涂有聚乙撑二氧噻吩‑聚(苯乙烯磺酸盐)(PEDOT：PSS)与多壁碳纳米管(MWCNT)复合气凝胶。本发明的2，4‑二氯酚电化学传感器，不仅能够成功检测2，4‑二氯酚，而且还具有灵敏度高、检测快速、稳定性好等特点，可用于2，4‑二氯酚浓度以及真样中2，4‑二氯酚的含量测定；本发明电化学传感器的制备方法，其制备成本低廉、工艺简单、操作简易。
Description
技术领域
本发明涉及电化学传感器技术领域，尤其涉及一种高灵敏度检测2，4- 二氯酚的电化学传感器及检测方法。
背景技术
近年来，酚类物质被广泛的应用在众多领域，2，4-二氯酚常被用作农药、石化产品、药品、除草剂等，造成严重的环境残留。2，4-二氯酚具有高毒性、致癌性和生物蓄积性，已被许多国家列为环境和人类健康的重大潜在威胁。因此，实现对2，4-二氯酚的灵敏检测对环境安全和公众健康有重要意义。传统检测2，4-二氯酚的方法为高效液相色谱法(HPLC)和气相色谱法(GC)，所使用的仪器复杂且笨重，运行成本比较高，样品制备过程复杂。
电化学传感器可实现经济、实用、高效、特异、灵敏、精确、快速、简便的检测与分析。目前已经有关对2，4-二氯酚的电化学检测的研究， Zhang等(Jin Zhanga，JianpingLei，Huangxian Jua，Chaoying Wang， Analytica Chimica Acta 786(2013)16-21)构建盐酸血红素修饰分子印迹电极，成功用于2，4-二氯酚的电化学检测，该传感器的线性响应范围为 5.0-100μM，检测限为1.6μM；Dong等(Dong Sheying，Suo Gaochao，Li Nan，ChenZhen，Peng Lei，Fu Yile，Yang Qin，Huang Tinglin，Sensors and Actuators B 222(2016)972-979)利用1，3，5-苯三甲酸铜(Cu3(BTC)2)的金属有机框架材料修饰碳糊电极，实现对2，4-二氯酚的有效检测。线性范围为0.04μM-1μM，检测限为9nM。然而，这些所报道的电极制备方法较为复杂，并且在检测2，4-二氯酚的灵敏度或线性范围方面有所欠缺。
因此，提供一种省时高效、价格低廉的、制备简单、尤其检测灵敏度高的2，4-二氯酚浓度电化学传感器是非常有价值的。
发明内容
本发明要解决的技术问题是提供一种检测灵敏度高、实用高效准确且价格低廉的、尤其是能够进行2，4-二氯酚高灵敏度检测的电化学传感器及检测方法。
为解决上述技术问题，本发明提供技术方案如下：
一方面，本发明提供一种高灵敏度检测2，4-二氯酚的电化学传感器，所述电化学传感器的电极修饰材料为将多壁碳纳米管(MWCNT)分散液注射于PEDOT：PSS水凝胶前驱体后，经冷冻干燥法制备得到的 PEDOT：PSS/MWCNT气凝胶。
进一步的，所述PEDOT：PSS/MWCNT气凝胶制备方法包括：
1)将PEDOT：PSS分散液和H2SO4水溶液混合，超声5-10分钟；
2)将上述混合溶液采用水热法，于聚四氟乙烯不锈钢高压釜中90℃加热3h，即得到所述PEDOT：PSS水凝胶前驱体；
3)将MWCNT分散液注射于凝胶状的PEDOT：PSS水凝胶前驱体中，静置5-10分钟；
4)将得到的PEDOT：PSS/MWCNT水凝胶前驱体于冷冻干燥机中干燥 24h，得到所述PEDOT：PSS/MWCNT气凝胶复合材料。
进一步的，所述步骤1)中，PEDOT：PSS分散液为固含量为1.3％， PEDOT：PSS质量比为1：2.5的分散液，用量为4mL。
进一步的，硫酸水溶液浓度为0.5mol/L，用量为1mL。
进一步的，所述步骤3)中，与每4mL PEDOT：PSS分散液形成水凝胶前驱体，MWCNT浓度为1mg/mL，用量为0.5-4mL。
进一步的，所述2，4-二氯酚的检测线性范围为0.008μM-15μM；最低检测限为0.003μM。
另一方面，本发明还提供一种上述高灵敏度检测2，4-二氯酚的电化学传感器的制备方法，将PEDOT：PSS/MWCNT气凝胶复合材料分散在水中，制备成浓度为1-2mg/L的分散液；然后，取5-10μL上述 PEDOT：PSS/MWCNT分散液滴涂到打磨干净的玻碳电极表面，60℃干燥，制得PEDOT：PSS/MWCNT气凝胶复合电极。
再一方面，本发明还提供一种上述高灵敏度检测2，4-二氯酚的电化学传感器用于检测2，4-二氯酚的使用方法，将待检测样品预处理后所得溶液通过标准加入法与0.2M的磷酸盐缓冲液等体积混合，利用所述电化学传感器对其2，4-二氯酚进行检测分析。
通过将不同浓度的2，4-二氯酚溶液分别加入pH为5.5的磷酸盐缓冲液中，利用PEDOT：PSS/MWCNT气凝胶电极结合差分脉冲伏安法对2，4- 二氯酚进行测定，得到线性关系。
优选地，所述电化学传感器还包括用于检测2，4-二氯酚的电解质溶液，所述电解质溶液为pH 5.5磷酸二氢钠-磷酸氢二钠缓冲溶液。
与现有技术相比，本发明的有益效果为：
1)本发明的2，4-二氯酚电化学传感器，不仅能够成功检测2，4-二氯酚，而且还具有灵敏度高、稳定性高、检测线性范围宽等特点，所制备的 PEDOT：PSS/MWCNT气凝胶修饰电极可用于2，4-二氯酚浓度以及真样中2，4-二氯酚的含量测定；
2)本发明电化学传感器的制备方法，其制备成本低廉、工艺简单、操作简易；检测线性范围为0.008μM-15μM；最低检测限可达0.003μM。
附图说明
图1为本发明实施例1制备的PEDOT：PSS/MWCNT气凝胶材料制备流程图；
图2为本发明实施例1制备的PEDOT：PSS/MWCNT气凝胶材料扫描电镜(SEM)图；
图3为本发明实施例1制备的PEDOT：PSS/MWCNT气凝胶材料透射电子显微镜(TEM)图；
图4为本发明实施例1制备的PEDOT：PSS/MWCNT气凝胶材料修饰的玻碳电极检测2，4-二氯酚的线性图；
图5为本发明实施例1制备的PEDOT：PSS/MWCNT气凝胶材料修饰的玻碳电极检测2，4-二氯酚的氧化峰电流与2，4-二氯酚浓度线性关系图；
图6为本发明实施例2制备的PEDOT：PSS/MWCNT气凝胶材料修饰的玻碳电极(c)与对比例1制备的MWCNT修饰的玻碳电极(a)和 PEDOT：PSS气凝胶修饰的玻碳电极(b)在铁氰化钾溶液中的循环伏安法电化学响应图。
具体实施方式
为使本发明的实施例需要解决的技术问题、技术方案和优点更加清楚，下面将结合具体实施例和附图进行详细描述。但本发明绝非限于这些例子。以下所述仅为本发明较好的实施例，仅仅用以解释本发明，并不能因此而理解为本发明专利范围的限制。应当指出的是，凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。因此，本发明专利的保护范围应以所附权利要求为准。
实施例1
一种高灵敏度检测2，4-二氯酚的电化学传感器及其制备方法：
PEDOT：PSS/MWCNT气凝胶制备方法包括如下步骤：1)将4mL PEDOT：PSS分散液和1mL H2SO4水溶液(1mg/L)混合，超声5-10分钟； 2)将上述混合溶液采用水热法，于聚四氟乙烯不锈钢高压釜中90℃加热 3h，得到所述PEDOT：PSS水凝胶前驱体；3)将3mL MWCNT分散液注射于凝胶状的PEDOT：PSS水凝胶前驱体中，静置5-10分钟；4)将得到的PEDOT：PSS/MWCNT水凝胶前驱体于冷冻干燥机中干燥24h，得到所述PEDOT：PSS/MWCNT气凝胶复合材料。
取5μL上述PEDOT：PSS/MWCNT气凝胶复合材料(1mg/L)滴涂到打磨干净的玻碳电极表面，60℃干燥，制得PEDOT：PSS/MWCNT气凝胶复合电极。
本发明制备的PEDOT：PSS/MWCNT气凝胶合成体系如图1所示，由 PEDOT：PSS水分散液经水热法制备得到PEDOT：PSS水凝胶前驱体，通过向PEDOT：PSS水凝胶前驱体中注射MWCNT悬浮液与冷冻干燥，得到MWCNT均匀依附分散于PEDOT：PSS气凝胶的复合材料。
本发明制备的PEDOT：PSS/MWCNT气凝胶修饰电极的扫描电子显微镜(SEM)图如图2所示，气凝胶表面显示均匀分散的二维管状结构 MWCNT，表明复合材料的成功制备。
本发明制备的PEDOT：PSS/MWCNT气凝胶的透射电子显微镜(TEM) 图如图3所示，表明在PEDOT：PSS气凝胶中分散有MWCNT。
2，4-二氯酚的电化学测定：不同浓度的2，4-二氯酚溶液分别加入pH为 5.5的磷酸盐缓冲液中，利用PEDOT：PSS/MWCNT气凝胶电极结合差分脉冲伏安法对2，4-二氯酚进行测定，如图4与图5所示，该复合材料修饰电极对2，4-二氯酚具有良好的线形关系(R2＝0.996)，且具有较宽的线性范围 (0.008μM-15μM)和较高的灵敏度和低检测限(0.003μM)，充分表明该新型传感电极能够成功检测未知浓度的2，4-二氯酚。
真样中2，4-二氯酚浓度的检测分析：自来水通过标准加入法与0.2M 的磷酸盐缓冲液等体积混合，然后加入0.1μM、1μM、10μM浓度的2，4- 二氯酚，利用PEDOT：PSS/MWCNT气凝胶修饰电极对其进行检测分析，结果表明0.096μM、0.989μM、10.213μM的2，4-二氯酚存在于检测溶液中，其回收率在96.0％到102.13％之间，表明构建的传感器用于2，4-二氯酚实际样品的检测分析是可行的。
对比例1
PEDOT：PSS气凝胶制备方法包括如下步骤：1)将4mL PEDOT：PSS 分散液和1mLH2SO4水溶液(0.5mol/L)混合，超声5-10分钟；2)将上述混合溶液采用水热法，于聚四氟乙烯不锈钢高压釜中90℃加热3h，得到所述PEDOT：PSS水凝胶前驱体；3)将得到的PEDOT：PSS水凝胶前驱体于冷冻干燥机中干燥24h，得到PEDOT：PSS气凝胶材料。
取5μL PEDOT：PSS气凝胶材料(1mg/L)与MWCNT悬浮液(1mg/L)，分别滴涂到打磨干净的玻碳电极表面，60℃干燥，制得PEDOT：PSS气凝胶修饰电极与MWCNT修饰电极。与PEDOT：PSS/MWCNT气凝胶修饰电极在铁氰化钾中的电化学行为进行研究如下。
铁氰化钾中的电化学行为分析：在含有5mM铁氰化钾(K3Fe(CN)6) 与亚铁氰化钾(K4Fe(CN)6)的0.1M氯化钾(KCl)溶液中，实施例1制得的PEDOT：PSS/MWCNT气凝胶修饰电极与对比例1制得的 PEDOT：PSS气凝胶修饰电极和MWCNT修饰电极结合循环伏安法对其电化学行为进行比较。如图6所示，在所有的CV曲线中，都观察到了一对可逆氧化还原峰，对应于[Fe(CN)6]3-/4-离子的氧化还原。其中， PEDOT：PSS/MWCNT气凝胶修饰电极相较于MWCNT修饰电极有更高的氧化还原峰电流。PEDOT：PSS/MWCNT气凝胶修饰电极相较于 PEDOT：PSS气凝胶修饰电极有更小的峰间距。上述结果表明经 PEDOT：PSS/MWCNT气凝胶复合材料具有更优的电化学可逆性与更快的电子转移效率，结合了单一材料的优点，PEDOT：PSS/MWCNT气凝胶修饰电极电化学性能得到提升。
本发明在制备PEDOT：PSS/MWCNT气凝胶复合材料修饰电极时，并不局限于实施例1中原材料的取量，使用3-5mL PEDOT：PSS分散液和 0.5-4mL的MWCNT混合制备PEDOT：PSS/MWCNT气凝胶复合材料修饰电极时，均具有较高的检测灵敏度，本发明不再一一列举。
综上可知，本发明的2，4-二氯酚电化学传感器，制备成本低廉、工艺简单、操作简易，且可用于2，4-二氯酚浓度以及真样中2，4-二氯酚的含量测定。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明所述原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (8)
1.一种高灵敏度检测2，4-二氯酚的电化学传感器，其特征在于，所述电化学传感器的电极修饰材料为将多壁碳纳米管(MWCNT)分散液注射于PEDOT∶PSS水凝胶前驱体后，经冷冻干燥法制备得到的PEDOT∶PSS/MWCNT气凝胶。
2.根据权利要求1所述的高灵敏度检测2，4-二氯酚的电化学传感器，其特征在于，所述PEDOT∶PSS/MWCNT气凝胶制备方法包括：
1)将PEDOT∶PSS分散液和H2SO4水溶液混合，超声5-10分钟；
2)将上述混合溶液采用水热法，于聚四氟乙烯不锈钢高压釜中90℃加热3h，即得到所述PEDOT∶PSS水凝胶前驱体；
3)将MWCNT分散液注射于凝胶状的PEDOT∶PSS水凝胶前驱体中，静置5-10分钟；
4)将得到的PEDOT∶PSS/MWCNT水凝胶前驱体于冷冻干燥机中干燥24h，得到所述PEDOT∶PSS/MWCNT气凝胶复合材料。
3.根据权利要求2所述的高灵敏度检测2，4-二氯酚的电化学传感器，其特征在于，所述步骤1)中，PEDOT∶PSS分散液为固含量为1.3％，PEDOT∶PSS质量比为1∶2.5的分散液，用量为4mL。
4.根据权利要求3所述的高灵敏度检测2，4-二氯酚的电化学传感器，其特征在于，硫酸水溶液浓度为0.5mol/L，用量为1mL。
5.根据权利要求2所述的高灵敏度检测2，4-二氯酚的电化学传感器，其特征在于，所述步骤3)中，与每4mL PEDOT∶PSS分散液形成水凝胶前驱体，MWCNT浓度为1mg/mL，用量为0.5-4mL。
6.根据权利要求1-5任一所述的高灵敏度检测2，4-二氯酚的电化学传感器，其特征在于，所述电化学传感器的2，4-二氯酚的检测线性范围为0.008μM-15μM；最低检测限为0.003μM 。
7.一种权利要求1-6任一所述的高灵敏度检测2，4-二氯酚的电化学传感器的制备方法，其特征在于，将PEDOT∶PSS/MWCNT气凝胶复合材料分散在水中，制备成浓度为1-2mg/L的分散液；然后，取5-10μL上述PEDOT∶PSS/MWCNT分散液滴涂到打磨干净的玻碳电极表面，60℃干燥，制得PEDOT∶PSS/MWCNT气凝胶复合电极。
8.一种权利要求1-6任一所述的高灵敏度检测2，4-二氯酚的电化学传感器的检测方法，其特征在于，将待检测样品预处理后所得溶液通过标准加入法与0.2M的磷酸盐缓冲液等体积混合，利用所述电化学传感器对其2，4-二-氯酚进行检测分析。
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