CN109298060B - 一种基于ito的羧基化多壁碳纳米管修饰电极的制备及应用该电极测定尿酸的方法 - Google Patents

一种基于ito的羧基化多壁碳纳米管修饰电极的制备及应用该电极测定尿酸的方法 Download PDF

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CN109298060B
CN109298060B CN201811215310.XA CN201811215310A CN109298060B CN 109298060 B CN109298060 B CN 109298060B CN 201811215310 A CN201811215310 A CN 201811215310A CN 109298060 B CN109298060 B CN 109298060B
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孙晶
甄雪
马龙飞
杨海波
郎明非
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Abstract

本发明涉及电化学分析技术领域,具体涉及一种基于ITO的羧基化多壁碳纳米管修饰电极的制备及应用该电极测定尿酸的方法。由自制电极为工作电极、Ag/AgCl电极为参比电极、铂丝为辅助电极及电化学工作站组成的电化学测定系统。自制电极以ITO玻璃为基底，用PDDA与PSS交替在ITO表面自组装成膜，在自组装层上均匀滴涂一层羧基化多壁碳纳米管。本发明的目的在于应用基于ITO的羧基化多壁碳纳米管修饰电极，建立一种测定尿酸的方法。即采用差分脉冲伏安法进行电测学测定、标准曲线法进行定量分析。该方法简单、测定成本低，对测定尿酸具有较高准确度、精密度，在尿酸检测领域有较高的应用价值。

Description

一种基于ITO的羧基化多壁碳纳米管修饰电极的制备及应用 该电极测定尿酸的方法
技术领域
本发明涉及电化学分析技术领域，具体涉及一种可用于尿酸测定的电极。
背景技术
生物分子尿酸是人体内嘌呤代谢的最终代谢产物。正常情况下，体内的尿酸大约有1200毫克并处于平衡状态。体内尿酸浓度偏高会引起痛风、心血管疾病、肾病等。尿酸目前的主要分析方法有高效液相色谱(HPLC)、传感器法、酶法、电化学分析法和光度法等，光谱法易受样品中存在的其它发色团的影响；色谱法样品处理过程过于繁琐；酶方法虽然选择性好，但价格昂贵，成本高，限制了它的使用范围。
发明内容
为弥补现有技术的不足，本发明提供一种简便、实用、低廉的快速检测尿酸的电极的制备方法和应用。
本发明采用的技术方案是：
(1)电极的制备：在清洁的ITO玻璃表面高分子自组装，涂覆羧基化多壁碳纳米管，制备基于ITO的羧基化多壁碳纳米管修饰电极；
(2)实际样品的测定：工作电极为基于ITO的羧基化多壁碳纳米管修饰电极，参比电极为Ag/AgCl电极，辅助电极为铂丝；将该三电极系统置于尿酸待测液中，测定浓度为4μmol/L～80μmol/L范围内的尿酸待测液的差分脉冲伏安曲线，用标准曲线法进行样品的定量分析。
由自制电极为工作电极，Ag/AgCl电极为参比电极，铂丝为辅助电极以及电化学工作站组成的电化学系统；自制电极以ITO玻璃为基底，用聚二丙烯基二甲基氯化铵(PDDA)与聚苯乙烯磺酸钠(PSS)交替在ITO玻璃表面自组装成膜，在自组装层上均匀滴涂一层羧基化多壁碳纳米管。
所述步骤(2)中电化学系统以pH为6.8、以浓度为0.05mol/L柠檬酸-柠檬酸钠、酒石酸-酒石酸钠、醋酸-醋酸钠或磷酸二氢钠-磷酸氢二钠作为支持电解质。于-0.1V～0.8V电位范围记录浓度为4μmol/L～80μmol/L范围内的尿酸待测液的差分脉冲伏安曲线。
更优选的，以0.05mol/L的磷酸二氢钠-磷酸氢二钠为支持电解质。
本发明所采用的电化学法具有高灵敏度、低成本等优点，多壁碳纳米管以其优越的物理和化学性能而在电化学领域广泛应用，碳纳米管的表面效应，使其表面原子活性高，比表面积大，且负电荷的碳纳米管表面与带正电荷的UA存在较强的静电吸引力，在电催化和分析化学领域中具有很好的应用前景，用它来修饰电极将使电极的真实表面积大大提高，为电化学反应提供充足的反应场所。本发明利用ITO玻璃良好的导电性，并结合羧基化多壁碳纳米管对尿酸的选择性催化作用，制得一种对尿酸具有良好电化学响应的电极。通过优化支持电解质种类、pH等参数，得到对尿酸具有较高的灵敏度、准确度和精密度的电化学分析方法，并把该方法应用于实际样品测定。该方法简单、测定成本低，对测定尿酸具有较高准确度、精密度，在尿酸检测领域有较高的应用价值。
附图说明
图1为基于ITO玻璃的羧基化多壁碳纳米管修饰电极的平面结构示意图。其中，图1中，1、ITO玻璃基片，2、PDDA-PSS高分子自组装层，3、羧基化多壁碳纳米管层。
图2为支持电解质溶液种类的优化实验图。
图3为pH值的优化曲线。
图4为不同浓度尿酸溶液的标准曲线。
具体实施方式
下面通过具体实施例详述本发明，但不限制本发明的保护范围。如无特殊说明，本发明所采用的实验方法均为常规方法，所用实验器材、材料、试剂等均可从化学公司购买。
实施例1
下述实施例基于ITO的羧基化多壁碳纳米管修饰电极的制备方法为：
ITO玻璃表面的清洁。将ITO玻璃切割成1cm×4cm，在去离子水中超声清洗30min，然后在丙酮中超声清洗30min，最后在无水乙醇中超声清洗30min。氮气吹干备用。
ITO玻璃表面高分子层自组装，具体步骤如下：
(1)将ITO玻璃导电层放入紫外臭氧清洗机中进行表面羟基化30min。
(2)将ITO玻璃放入1mg/mL PDDA溶液中浸泡3min，拿出后用去离子水清洗表面多余溶液，氮气吹干，然后放入1mg/mLPSS溶液中浸泡3min，拿出后用去离子水清洗表面多余溶液，氮气吹干。此为一层完整的自组装层。该自组装层共组装6层。
(3)基于ITO的羧基化多壁碳纳米管修饰电极的制备。在自组装好的ITO玻璃导电层滴涂1mg/mL羧基化多壁碳纳米管乙醇溶液20μL，晾干。涂3次。晾干备用。
由自制电极为工作电极，Ag/AgCl电极为参比电极，铂丝为辅助电极以及电化学工作站组成的电化学系统；自制电极以ITO玻璃为基底，用PDDA与PSS交替在ITO玻璃表面自组装成膜，在自组装层上均匀滴涂一层羧基化多壁碳纳米管。如图1所示为基于ITO玻璃的羧基化多壁碳纳米管修饰电极的平面结构示意图。
如图2所示，探究了以柠檬酸-柠檬酸钠、酒石酸-酒石酸钠、醋酸-醋酸钠和磷酸二氢钠-磷酸氢二钠(浓度为0.05mol/L，并用氢氧化钠调节pH值为6.82)作为支持电解质时40μmol/L尿酸溶液的差分脉冲伏安曲线。结果表明，在磷酸二氢钠-磷酸氢二钠溶液中尿酸溶液的峰电流最大。
如图3所示为pH值的优化曲线。当pH值为6.8时，差分脉冲伏安曲线峰电流最高。
利用本发明电极检测浓度范围为4μmol/L～80μmol/L的尿酸溶液，在最佳的实验条件下，记录电位在-0.1V～0.8V范围内的差分脉冲伏安曲线，并分析曲线峰电流值。利用origin软件，做出标准曲线，该曲线方程为：y＝2.26741×10-5+9.81313×10-7x，相关系数为0.99495。
实施例2
样品：55μmol/L尿酸标准溶液。
测定方法：
采用实施例1制备的三电极体系：基于ITO的羧基化多壁碳纳米管修饰电极为工作电极，Ag/AgCl电极为参比电极，铂丝为辅助电极，以pH为6.8的0.05mol/L磷酸二氢钠-磷酸氢二钠溶液为支持电解质，采用差分脉冲伏安法进行电测学测定，记录尿酸在-0.1～0.8V的区间内的差分脉冲伏安曲线，采用标准曲线法进行定量分析。
实验平行测定10次，得到氧化峰峰电流平均值为7.54×10-5A，代入线性回归方程y＝2.26741×10-5+9.81313×10-7x计算出所测溶液中尿酸的的平均含量为53.77μmol/L。标准值(55μmol/L)与测定值的相对误差：2.2％；10次平行测定的相对标准偏差RSD值为2.69％。
实施例3
样品：20μmol/L尿酸标准溶液。
测定方法：
采用三电极体系：基于ITO的羧基化多壁碳纳米管修饰电极为工作电极，Ag/AgCl电极为参比电极，铂丝为辅助电极，以pH为6.8的0.05mol/L磷酸二氢钠-磷酸氢二钠溶液为支持电解质，采用差分脉冲伏安法进行电测学测定，记录尿酸在-0.1～0.8V的区间内的差分脉冲伏安曲线，采用标准曲线法进行定量分析。
实验平行测定10次，得到氧化峰峰电流平均值为4.378×10-5A，代入线性回归方程y＝2.26741×10-5+9.81313×10-7x计算出所测溶液中尿酸的的平均含量为21.50μmol/L。标准值(20μmol/L)与测定值的相对误差：7.5％；10次平行测定的相对标准偏差RSD值为1.37％。
实施例4
样品：5μmol/L尿酸标准溶液。
测定方法：
采用三电极体系：基于ITO的羧基化多壁碳纳米管修饰电极为工作电极，Ag/AgCl电极为参比电极，铂丝为辅助电极，以pH为6.8的0.05mol/L磷酸二氢钠-磷酸氢二钠溶液为支持电解质，采用差分脉冲伏安法进行电测学测定，记录尿酸在-0.1～0.8V的区间内的差分脉冲伏安曲线，采用标准曲线法进行定量分析。
实验平行测定10次，得到氧化峰峰电流平均值为2.769×10-5A，代入线性回归方程y＝2.26741×10-5+9.81313×10-7x计算出所测溶液中尿酸的的平均含量为5.11μmol/L。标准值(5μmol/L)与测定值的相对误差：2.2％；10次平行测定的相对标准偏差RSD值为2.88％
以上所述，仅为本发明创造较佳的具体实施方式，但本发明创造的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明创造披露的技术范围内，根据本发明创造的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明创造的保护范围之内。

Claims (1)

1.一种基于ITO的羧基化多壁碳纳米管修饰电极测定尿酸的方法，其特征在于，以ITO玻璃为基底，用聚二丙烯基二甲基氯化铵PDDA 与聚苯乙烯磺酸钠PSS 交替在ITO玻璃表面自组装成膜，在自组装层上均匀滴涂一层羧基化多壁碳纳米管，得到基于ITO的羧基化多壁碳纳米管修饰电极；包括以下步骤：
(1)电极的制备：ITO玻璃表面的清洁，将ITO玻璃切割成1cm×4cm，在去离子水中超声清洗30min，然后在丙酮中超声清洗30min，最后在无水乙醇中超声清洗30min，氮气吹干备用；
ITO玻璃表面高分子层自组装，具体步骤如下：
(1.1)将ITO玻璃导电层放入紫外臭氧清洗机中进行表面羟基化30min；
(1.2)将ITO玻璃放入1mg/mL PDDA溶液中浸泡3min，拿出后用去离子水清洗表面多余溶液，氮气吹干，然后放入1mg/mL PSS溶液中浸泡3min，拿出后用去离子水清洗表面多余溶液，氮气吹干，此为一层完整的自组装层，该自组装层共组装6层；
(1.3)基于ITO的羧基化多壁碳纳米管修饰电极的制备，在自组装好的ITO玻璃导电层滴涂1mg/mL羧基化多壁碳纳米管乙醇溶液20μL，晾干，涂3次，晾干备用，得到基于ITO的羧基化多壁碳纳米管修饰电极；
(2)实际样品的测定：工作电极为基于ITO的羧基化多壁碳纳米管修饰电极，参比电极为Ag/AgCl电极，辅助电极为铂丝，以pH为6.8、以浓度为0.05mol/L磷酸二氢钠-磷酸氢二钠作为支持电解质；将该三电极系统置于尿酸待测液中，于-0.1V～0.8V电位范围测定浓度为4μmol/L～80μmol/L范围内的尿酸待测液的差分脉冲伏安曲线，用标准曲线法进行样品的定量分析，该曲线方程为：y＝2.26741×10-5+9.81313×10-7x，相关系数为0.99495。
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