CN104101631A - 一种用于检测重金属残留的电化学传感器的制备方法 - Google Patents
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Abstract
本发明涉及一种用于检测重金属残留的电化学传感器的制备方法。本发明将合成的涂覆有席夫碱络合物的四氧化三铁纳米颗粒嵌入到碳糊电极上，从而制备了一种新型的改性电极，并用该电极构建的电化学传感器，用于镉、铜和汞等重金属的痕量检测。四氧化三铁纳米颗粒具有良好的化学热力稳定性、电催化活性、大的比表面积和高导电性等特征，大环席夫碱具有优良的检测选择性，使两者对本发明涉及的电化学传感器产生显著的改性效应。本发明涉及的电化学传感器为水和食品中镉、铜和汞的同时检测提供了一种简单、快速、灵敏和选择性高的方法。
Description
技术领域
本发明涉及一种电化学传感器的制备方法，尤其涉及一种可用于同时检测水和食品中的镉、铜和汞等重金属离子的基于席夫碱涂覆四氧化三铁纳米颗粒改性碳糊电极的制备方法。
背景技术
无机离子污染物对人类健康和自然环境都有重要的影响，重金属离子对食物链中的植物群和动物群，包括人类都有毒性效应。近年来人们越来越关注食品质量和安全，因此对食品中有毒元素的检测显得更加重要。检测样品中重金属离子的方法有很多种，通常用来检测不同浓度重金属离子的方法有原子吸收光谱(AAS)、离子耦合光发射光谱(ICP-OES)、离子耦合质谱(ICP-MS)、中子活化分析(NAA)、X射线荧光(XRF)、离子色谱(IC)和电化学方法(如基于不同电极的提溶伏安法和差示脉冲伏安法)。检测方法的选择主要依赖于如下参数：成本、灵敏度、简单性、检测限、基质的物理性能和分析仪器的可获得性。
在重金属离子中，汞对人体的生理功能是具有危害性的，镉会引起高血压、肝病和脑神经损坏，铜是人类新陈代谢的必需元素但是如果含量太高也是有害的。过量的镉、铜和汞附着在细胞膜上会抑制细胞壁的传输功能，因此对这些重金属离子的控制是非常重要的。
基于不同电极的电化学传感器已经应用于重金属离子的痕量检测，通常使用的电极有铂、金、玻璃碳、滴汞电极以及修饰改性的石墨和碳糊电极。
但现有技术中用于重金属离子痕量检测的，基于不同电极的电化学传感器中，并没有一种价格低廉、节省时间、检测灵敏度高、重金属选择性高，且可同时检测镉、铜和汞的电化学传感器。
发明内容
改性电极能够有效及有选择性地对靶对样品中有机和无机化合物检测，已经广泛用于传感器，本发明采用改性电极的方法来制备检测重金属的电化学传感器。
席夫碱是一种用于金属离子传感器的非常优良的改性剂，因其对电极表面金属离子的高聚集作用，从而在伏安检测中提供低的检测限。
四氧化三铁具有良好的化学热力稳定性、电催化活性、大的比表面积和高导电性等特征，成为用于碳糊电极改性的优良改性剂。四氧化三铁改性的电极，即磁改性电极中的磁性微米颗粒，能够附着在电极的表面或者嵌入到电极内部作为电子导体，可保持永久的磁场；永久磁场效应对电子转移机理、增加系统效率、电化学流动性都有显著的影响，还能多方面影响电极系统，提高同质和异质电子转移速率、增强传质、提高电沉积质量、控制电势分布和电流、减小腐蚀速率、抑制电子自旋熵变并且降低活化能垒。
本发明采用的方法是：将席夫碱涂覆到四氧化三铁纳米颗粒的表面，改性碳糊电极，组成碳糊电极的选择剂，从而制备出电化学传感器用以检测水和食品中的镉、铜和汞等重金属离子的含量。
本发明涉及的电化学传感器，所使用的席夫碱能够同靶向离子形成络合物，用来同时检测镉、铜和汞，由于席夫碱络合物和被检测离子之间的相互作用，将席夫碱涂覆到四氧化三铁纳米颗粒的表面能够显著提高离子检测的检测限、灵敏度和选择性。
本发明所使用的席夫碱包括但不限于单席夫碱、双席夫碱、大环席夫碱，优选为大环席夫碱。
本发明所涉及的制备方法步骤如下：
(1)席夫碱络合物的合成：1～3mmol(0.186～0.558g)哌嗪溶解到200～600mL甲醇中形成溶液，然后在搅拌下逐滴加入到溶解有1～3mmol(0.152～0.456g)2-羟基-3-甲氧基苯甲醛的热的100～300mL甲醇溶液中。混合溶液搅拌加热回流4～7h，将黄色沉淀物滤出，用冷的甲醇洗涤，真空干燥得到席夫碱络合物。
(2)四氧化三铁纳米颗粒的制备和涂覆：四氧化三铁纳米颗粒用Fe2+和Fe3+溶液共沉淀的方法制备，0.2～0.6g席夫碱络合物溶解在25～75mL甲醇中，与0.2～0.6g四氧化三铁纳米颗粒混合，将混合体系的pH调到6.1～6.3，然后在55～60℃下反应5～8h，固体相滤出、洗涤，室温下干燥得到涂覆席夫碱络合物的四氧化三铁纳米颗粒。
(3)改性碳糊电极的制备：制备0.4～1g含有1％(重量百分比)席夫碱络合物涂覆四氧化三铁纳米颗粒，76～80％(重量百分比)石墨粉末和23～19％(重量百分比)石蜡的混合物，再将混合物装入到直径0.5～1mm，长度2.0～4.0cm的毛细管中，得到改性碳糊电极。
本发明设计了一种基于席夫碱络合物涂覆四氧化三铁纳米颗粒修饰碳糊电极的电化学传感器。这种传感器具有响应快速和长期稳定性的特点，被成功用于不同水样品和食品样品中镉、铜和汞离子的同时检测。四氧化三铁具有良好的化学热力稳定性、电催化活性、大的比表面积和高导电性等优良性能，使其对传感器产生显著的改性效应。席夫碱络合物能够选择性的和被检测重金属离子相互作用，赋予传感器优良的检测选择性，四氧化三铁和席夫碱的优良性能在本发明的传感器中相互结合，为重金属离子的检测提供了一种省时、简单有效、高灵敏度和选择性的方法。
本发明所涉及的新型电化学传感器为水和食品中的镉、铜和汞的同时检测提供了一种简单、快速、灵敏和选择性高的方法。
具体实施方式
为了加深对本发明的理解，下面结合实施对本发明作进一步详述。
一种用于同时检测水和食品中镉、铜和汞重金属离子的电化学传感器的制备方法，其步骤如下：
(1)席夫碱络合物的合成：1mmol(0.186g)哌嗪溶解到200mL甲醇中形成溶液，然后在搅拌下逐滴加入到溶解有1mmol(0.152g)2-羟基-3-甲氧基苯甲醛的热的100mL甲醇溶液中，混合溶液搅拌加热回流4h，将黄色沉淀物滤出，用冷的甲醇洗涤，然后真空干燥得到席夫碱络合物。
(2)四氧化三铁纳米颗粒的制备和涂覆：四氧化三铁纳米颗粒用Fe2+和Fe3+溶液共沉淀的方法制备，取0.2g席夫碱络合物溶解在25mL甲醇中，然后与0.2g四氧化三铁纳米颗粒混合，将混合体系的pH调到6.3，在60℃下反应8h。固体相滤出、洗涤然后室温下干燥得到涂覆席夫碱络合物的四氧化三铁纳米颗粒。
(3)改性碳糊电极的制备：制备0.4g含有1％(重量百分比)席夫碱络合物涂覆四氧化三铁纳米颗粒，76％(重量百分比)石墨粉末和23％(重量百分比)石蜡的混合物，再将混合物装入到直径1mm，长度4.0cm的毛细管中。
Claims (9)
1.一种基于席夫碱涂覆四氧化三铁纳米颗粒改性碳糊电极用于检测重金属残留的电化学传感器的制备方法，其步骤如下：
(1)席夫碱络合物的合成：1～3mmol(0.186～0.558g)哌嗪溶解到200～600mL甲醇中形成溶液，然后在搅拌下逐滴加入到溶解有1～3mmol(0.152～0.456g)2-羟基-3-甲氧基苯甲醛的100～300mL甲醇溶液中，混合溶液搅拌加热回流4～7h，将黄色沉淀物滤出，用冷的甲醇洗涤，再真空干燥得到席夫碱络合物；
(2)四氧化三铁纳米颗粒的制备和涂覆：四氧化三铁纳米颗粒用Fe2+和Fe3+溶液共沉淀的方法制备，0.2～0.6g席夫碱络合物溶解在25～75mL甲醇中然后与0.2～0.6g四氧化三铁纳米颗粒混合，将混合体系的pH调到6.1～6.3，然后在55～60℃下反应5～8h，固体相滤出、洗涤，室温下干燥得到涂覆席夫碱络合物的四氧化三铁纳米颗粒；
(3)改性碳糊电极的制备：制备0.4～1g混合物，所述混合物包括1％(重量百分比)的席夫碱络合物涂覆四氧化三铁纳米颗粒、76～80％(重量百分比)的石墨粉末以及23～19％(重量百分比)的石蜡，将混合物装入到直径0.5～1mm，长度2.0～4.0cm的毛细管中，得到改性碳糊电极。
2.根据权利要求1所述的电化学传感器的制备方法，其特征在于：步骤(1)中所述溶解有2-羟基-3-甲氧基苯甲醛的甲醇溶液为热溶液，体积为100mL。
3.根据权利要求1所述的电化学传感器的制备方法，其特征在于：步骤(1)中所述混合溶液搅拌加热回流的时间为8h。
4.根据权利要求1所述的电化学传感器的制备方法，其特征在于：步骤(1)中所述席夫碱络合物与四氧化三铁纳米颗粒混合的比例为1:1。
5.根据权利要求4所述的电化学传感器的制备方法，其特征在于：所述席夫碱络合物与四氧化三铁纳米颗粒混合的质量都是0.2g。
6.根据权利要求1所述的电化学传感器的制备方法，其特征在于：步骤(3)中所述混合物中，席夫碱络合物涂覆的四氧化三铁纳米颗粒、石墨粉末和石蜡的重量比为：1:80:19。
7.根据权利要求1所述的电化学传感器的制备方法，其特征在于：步骤(3)中所述混合物中，席夫碱络合物涂覆的四氧化三铁纳米颗粒、石墨粉末和石蜡的重量比为：1:76:23。
8.根据权利要求1～7所述的任一电化学传感器的制备方法，其特征在于：所述席夫碱为单席夫碱、双席夫碱或大环席夫碱。
9.根据权利要求8所述的电化学传感器的制备方法，其特征在于：所述席夫碱为大环席夫碱。
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