CN110865108B - 一种基于金属有机骨架的特异性修饰电极及其制备和应用 - Google Patents
一种基于金属有机骨架的特异性修饰电极及其制备和应用 Download PDFInfo
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Abstract
本发明提供了一种基于金属有机骨架的特异性修饰电极的构建方法，是将氨基化的金属有机框架与还原氧化石墨烯超声分散于N,N‑二甲基甲酰胺中，并将分散液滴涂在打磨好的玻碳电极表面制得修饰电极rGO‑NH2‑Cu3(btc)2/GCE；以rGO‑NH2‑Cu3(btc)2/GCE修饰电极为工作电极组成三电极体系；插入含HAuCl4的H2SO4溶液中，采用恒电位沉积法将金纳米粒子沉积到电极表面，制得特异性修饰电极Au/rGO‑NH2‑Cu3(btc)2/GCE。该修饰电极能够将对乙酰氨基酚和对氨基酚的氧化峰完全分开，实现了两者的同时检测；而且检测方法快速简便，具有良好的抗干扰性和稳定性。
Description
技术领域
本发明涉及一种基于金属有机骨架的特异性修饰电极的构建方法，主要用于对乙酰氨基酚和对氨基酚的检测，属于电化学传感器和电化学分析技术领域。
背景技术
作为镇痛和感冒药品，扑热息痛（ACOP）（N-乙酰基-对氨基苯酚或对乙酰氨基酚）主要用于缓解发烧，头痛，关节炎，术后疼痛和背痛相关的中度疼痛。但是，过量的对乙酰氨基酚的毒性代谢物在体内积累可能导致严重的后果，有时甚至造成致命的肝毒性，胰腺和皮肤的发炎。4-氨基苯酚（4-AP）是ACOP的主要水解降解产物。作为ACOP的合成中间体或降解产物，4-AP具有明显的肾毒性和致畸作用。因此，开发一种简便、灵敏、准确的方法来检测ACOP和4-AP已引起广大研究者的研究兴趣。目前为止，已报道了各种不同的检测ACOP和4-AP的分析技术，例如，分光光度法，高效液相色谱，滴定法，化学发光，荧光光度法，毛细管电泳等。但是这些方法存在耗时长，样品预处理成本高，灵敏度低等缺点。电化学方法具有操作简单，响应速度快，选择性高等优点，在分子及氨基酸的检测方面具有明显的优势。但是，单一的玻碳电极对ACOP和4-AP的电化学响应并不明显。所以，引入一些电极修饰材料以提高裸电极对检测ACOP和4-AP的灵敏度是很有必要的。
氧化石墨烯，一种由sp2杂化碳原子组成的二维片状结构，一经发现就引起了人们的极大关注。由于其独特的性能，例如具有大的表面积、优异的机械强度、良好的导电性、高度的柔韧性，成为构建电化学传感器的主要材料。然而，由于范德华力相互作用和π-π堆积，氧化石墨烯在水中易发生团聚，这便限制了它们在传感器方面的进一步应用。通过不同的方法对氧化石墨烯进行表面改性，可以提高其在水中的分散性，使其具有更好的生物相容性，拓宽其运用价值。
金属有机骨架（MOFs）是一类由金属离子（或金属簇）和有机配体组成的高度有序的多孔材料。由于其有序结构，大的比表面积，均匀可调的空腔和特定的化学性质近年来引起了人们的极大关注，目前已广泛应用于各种领域，如气体吸附，超级电容器，药物传输，催化，传感器，电池等方面。贵金属纳米粒子因具有良好的导电性和优异的催化活性，被广泛用于电化学传感器的电极材料的制备中。因此，构建一种基于金属有机骨架的特异性修饰电极实现对乙酰氨基酚和对氨基酚同时检测，在实际应用中具有十分重要的意义。
发明内容
本发明的目的是提供基于一种基于金属有机骨架的特异性修饰电极的制备方法；
本发明的另一目的是提供上述构建的特异性修饰电极同时检测对乙酰氨基酚和对氨基酚的具体应用。
一、基于金属有机骨架的特异性修饰电极
本发明特异性修饰电极的构建方法，包括以下步骤：
（1）氨基化金属有机框架材料NH2-Cu3(btc)2)的制备：将均苯三酸、2-氨基对苯二甲酸充分分散于无水N,N-二甲基甲酰胺和乙醇的混合液中，再加入硝酸铜水溶液搅拌0.5~1h；然后在80~90℃下水热反应20~30小时；冷却至室温，过滤，用N,N-二甲基甲酰胺和乙醇洗涤，50~70℃下真空干燥，得到NH2-Cu3(btc)2。所述无水N,N-二甲基甲酰胺和乙醇的混合液中，N,N-二甲基甲酰胺与乙醇的体积比为1.5:1~1:1。均苯三酸与2-氨基对苯二甲酸的质量比为3.5:1~3:1；均苯三酸与硝酸铜的质量比为1:0.3~1:0.5。
（2）修饰电极rGO-NH2-Cu3(btc)2/GCE的制备：将氨基化金属有机框架NH2-Cu3(btc)2与氧化石墨烯rGO分散于N,N-二甲基甲酰胺中，形成浓度2~2.5mg/mL的分散液，再将该分散液滴涂在打磨好的玻碳电极表面，在红外灯下干燥，制得修饰电极rGO-NH2-Cu3(btc)2/GCE。其中氨基化金属有机框架NH2-Cu3(btc)2与还原氧化石墨烯rGO的质量比为1.5:1~1:1。
（3）特异性修饰电极Au/rGO-NH2-Cu3(btc)2/GCE的制备：以rGO-NH2-Cu3(btc)2/GCE修饰电极为工作电极，与铂电极、饱和甘汞电极组成三电极体系；插入含HAuCl4的H2SO4溶液中，采用恒电位沉积法将金纳米粒子沉积到电极表面，制得特异性修饰电极Au/rGO-NH2-Cu3(btc)2/GCE。H2SO4溶液的浓度为0.1~0.15M；HAuCl4的浓度为2~2.5mM；恒电位沉积的条件为：沉积电位范围为-0.4~0.1V，沉积时间为60~100s。
二、Au/rGO-NH2-Cu3(btc)2/GCE修饰电极的形貌与结构分析
1、红外光谱分析
图1为氧化石墨烯（GO），还原氧化石墨烯（rGO），氨基化的金属有机框架(NH2-Cu3(btc)2)的红外光谱图。由图1可见，与GO相比，RGO在1725cm-1和1050cm-1处对应的C=O以及C-O的特征峰消失，说明GO被还原为rGO。另外在曲线c中，3424cm-1是N-H的对称伸缩振动，1641cm-1是C=O的伸缩振动，1445cm-1是有机配体中苯环的骨架振动，1107cm-1是C-N的伸缩振动，725cm-1是Cu-O的特征吸收，由此说明NH2-Cu3(btc)2成功合成。
2、扫描电镜分析
图2为（a）NH2-Cu3(btc)2，（b）rGO和（c）Au/NH2-Cu3(btc)2-rGO/GCE的扫描电镜图(SEM)。从图2a中可以看出，NH2-Cu3(btc)2呈现出规则的正八面体，而rGO的形貌是典型的片层结构（图2b）。另外，从图2c中可以明显观察到最终的金属有机骨架的特异性修饰电极(Au/NH2-Cu3(btc)2-rGO/GCE)的形貌中NH2-Cu3(btc)2附着在片层的rGO上，说明材料的复合是成功的。
3、X射线分析
图3为NH2-Cu3(btc)2和rGO的X射线衍射图（XRD）。图中在2θ为6.72°，11.61°，13.45°，14.68°，19.09°，20.25°，23.31°，25.89°和29.22°出现的衍射峰对应于NH2-Cu3(btc)2的(200)， (220)，(222)，(400)，(331)，(440)，(600)，(731)和(751)晶面。另外在rGO的XRD谱图中，在25°和44°分别对应于石墨典型的(002)和(111)晶面，由此进一步说明材料合成成功。
三、Au/NH2-Cu3(btc)2-rGO/GCE检测乙酰氨基酚和对氨基酚
1、检测方法
以Au/NH2-Cu3(btc)2-rGO/GCE为工作电极，与铂电极和饱、甘汞电极组成三电极体系，放入含对乙酰氨基酚和对氨基酚的磷酸缓冲溶液中（pH=8），采用差示脉冲伏安法进行扫描，扫描电位范围为-0.3~0.7V；得到不同浓度的对乙酰氨基酚和对氨基酚的DPV图，并采用origin软件绘制电化学传感器在不同浓度下对乙酰氨基酚和对氨基酚的响应电流与其浓度的线性关系图。
图4为在对氨基酚浓度为60μM时，不同浓度的对乙酰氨基酚在Au/NH2-Cu3(btc)2-rGO/GCE上的DPV响应。从图4中可以看出随着对乙酰氨基酚浓度的增大，其氧化峰电流逐渐增大，而对氨基酚的电流基本保持不变，说明所制备的电化学传感器可以检测对乙酰氨基酚。
图5为对乙酰氨基酚氧化峰电流与其浓度的线性关系图。从图5可见，在4~102μM的浓度范围内，对乙酰氨基酚氧化峰电流与其浓度的线性关系为：Ip=-0.3094c(ACOP)+0.1836；在102~300μM的浓度范围内，对乙酰氨基酚氧化峰电流与其浓度的线性关系为：Ip=0.0797c(ACOP)-23.8837。而且对乙酰氨基酚的浓度范围4~300μM，检测限为0.988μM（S/N=3）。
图6为对乙酰氨基酚浓度为40μM时，不同浓度的对氨基酚在Au/NH2-Cu3(btc)2-rGO/GCE上的DPV响应。图6显示了当对氨基酚的浓度逐渐增大时，其峰电流强度也随之增强，因此该传感器也可以实现对氨基酚的定量检测。
图7为对氨基酚氧化峰电流与其浓度的线性关系图。由图7可知，对氨基酚氧化峰电流与其浓度的线性关系：在4~500μM浓度范围内，对氨基酚氧化峰电流与其浓度成如下线性关系：Ip(μA)=0.0781c(4-AP)-0.7779 （R2 =0.9986），检测限为1.05μM（S/N=3）。
2、抗干扰能力测试
将Au/NH2-Cu3(btc)2-rGO/GCE为修饰电极、铂电极作为对电极，饱和甘汞电极为参比电极的三电极体系插入分别含Na+、K+、Mg2+、Ca2+、Cl- 、葡萄糖、柠檬酸、L-抗坏血酸、谷氨酸、苯酚、茶碱的对乙酰氨基酚和多巴胺的混合溶液中，在优化好的实验条件下（优化的实验条件为：NH2-Cu3(btc)2和rGO的质量比为2:2，NH2-Cu3(btc)2-rGO分散液的滴涂量为4微升，电沉积金纳米粒子的沉积时间为80s，沉积电压为-0.2V，pH为8）进行扫描，考察干扰物质对对乙酰氨基酚、对氨基酚电流的影响的百分比。
图8和图9为干扰物质对对乙酰氨基酚、对氨基酚峰电流的影响的百分比。可以看出，本Au/NH2-Cu3(btc)2-rGO/GCE修饰电极对各种阴阳离子和有机物均有较强的抗干扰能力。
3、稳定性测试
将以Au/NH2-Cu3(btc)2-rGO/GCE为修饰电极、铂电极为对电极，饱和甘汞电极为参比电极的三电极体系插入对乙酰氨基酚和对氨基酚的混合溶液中，在优化好的实验条件下进行循环伏安法扫描50圈，其响应信号分别保持原来的92.87%，94.93%（图10），说明该传感器具有良好的稳定性。
综上所述，本发明构建的Au/NH2-Cu3(btc)2-rGO/GCE电化学传感器具有特异性识别功能，能够将对乙酰氨基酚和对氨基酚的氧化峰完全分开，且不会相互干扰，实现了对乙酰氨基酚和对氨基酚的同时检测；而且检测方法快速简便，具有良好的抗干扰性和稳定性。
附图说明
图1为氧化石墨烯（GO），还原氧化石墨烯（rGO），氨基化的金属有机框架(NH2-Cu3(btc)2)的红外光谱图；
图2为NH2-Cu3(btc)2，rGO和Au/NH2-Cu3(btc)2-rGO/GCE的扫描电镜图（SEM）；
图3为NH2-Cu3(btc)2和rGO的X射线衍射图（XRD）；
图4为在对氨基酚浓度为60μM时，不同浓度的对乙酰氨基酚在Au/NH2-Cu3(btc)2-rGO/GCE上的DPV响应；
图5为对乙酰氨基酚氧化峰电流与其浓度的线性关系图；
图6为对乙酰氨基酚浓度为40μM时，不同浓度的对氨基酚在Au/NH2-Cu3(btc)2-rGO/GCE上的DPV响应；
图7为对氨基酚氧化峰电流与其浓度的线性关系图；
图8为一些潜在干扰物质对对乙酰氨基酚电流的影响的百分比；
图9为一些潜在干扰物质对对氨基酚峰电流的影响的百分比；
图10为Au/NH2-Cu3(btc)2-rGO/GCE的稳定性的循环伏安图。
具体实施方式
下面通过具体实施例对本发明Au/NH2-Cu3(btc)2-rGO/GCE电化学传感器的制备以及检测对乙酰氨基酚和对氨基酚的具体应用做详细说明。
实施例1、Au/NH2-Cu3(btc)2-rGO/GCE的构建
（1）NH2-Cu3(btc)2的制备：取1.22g硝酸铜加入到8.5mL离子水中；取0.58g 均苯三酸、0.18g 2-氨基对苯二甲酸，加入到17mL N,N-二甲基甲酰胺和乙醇的混合液中（各8.5mL）。在磁力搅拌0.5h；将溶液转移到装有聚四氟乙烯内衬的钢制高压釜中，保持反应温度在85℃下反应24h，冷却至室温，过滤，用N,N-二甲基甲酰胺和乙醇洗涤，在60℃下真空干燥，得到NH2-Cu3(btc)2；
（2）rGO的制备：将300mgGO加入到含有100mLH2O的圆底烧瓶中，超声分散2h，将3mLN2H4加入到悬浮液中，并将悬浮液在95℃下搅拌24h，冷却室温，过滤并分别用去离子水和乙醇洗涤，将产物在60℃下真空干燥，制得还原氧化石墨烯（rGO）；
（3）rGO-NH2-Cu3(btc)2/GCE修饰电极的制备：将2mg NH2-Cu3(btc)2，2mg rGO超声分散于体积为2mL N,N-二甲基甲酰胺中，再将该分散液（4微升）滴涂在打磨好的玻碳电极表面，在红外灯下干燥，制得rGO-NH2-Cu3(btc)2/GCE修饰电极；
（4）Au/rGO-NH2-Cu3(btc)2/GCE修饰电极的制备：以rGO-NH2-Cu3(btc)2/GCE修饰电极为工作电极、铂电极为对电极，饱和甘汞电极为参比电极，插入含HAuCl4（2.43 mM）的H2SO4（0.1M）溶液中，采用恒电位沉积法将金纳米粒子沉积到电极表面，制得Au/rGO-NH2-Cu3(btc)2/GCE修饰电极。恒电位沉积法的条件为：沉积电压-0.2V，沉积时间80s。
实施例2、Au/NH2-Cu3(btc)2-rGO/GCE电化学传感器同时检测对乙酰氨基酚和对氨基酚
（1）样品溶液的配制：分别称取37.8mg对乙酰氨基酚，27.3mg对氨基酚，用pH为8的磷酸缓冲溶液分别定容到25mL，即配制好浓度为1×10-2M的母液。移取0.25 mL的母液进行稀释，配制得到对乙酰氨基酚浓度为100μM，对氨基酚浓度为100μM的样品溶液；
（2）检测对乙酰氨基酚和对氨基酚：以实施例1制备的Au/NH2-Cu3(btc)2-rGO/GCE修饰电极，铂电极和饱和甘汞电极为三电极体系，放入含对乙酰氨基酚和对氨基酚的磷酸缓冲溶液中（pH=8），采用差示脉冲伏安法进行扫描，扫描电位范围为-0.3~0.7V；
（3）检测结果：根据对乙酰氨基酚氧化峰电流与其浓度的线性关系、对氨基酚氧化峰电流与其浓度的线性关系，计算得到对乙酰氨基酚的浓度为100μM；对氨基酚的浓度为100μM；乙酰氨基酚氧化峰电流与其浓度的线性关系为：Ip=0.3094c(ACOP)+0.1836；对氨基酚氧化峰电流与其浓度的线性关系为：Ip(μA)=0.0781c(4-AP)-0.7779。
实施例3、Au/NH2-Cu3(btc)2-rGO/GCE电化学传感器同时检测对乙酰氨基酚和对氨基酚
（1）样品溶液的配制：分别称取37.8mg对乙酰氨基酚，27.3mg对氨基酚，用pH为8的磷酸缓冲溶液分别定容到25mL，即配制好浓度为1×10-2M的母液。移取0.5mL的母液进行稀释，配制得到对乙酰氨基酚浓度为200μM，对氨基酚为200μM的样品溶液；
（2）检测对乙酰氨基酚和对氨基酚：以实施例1制备的Au/NH2-Cu3(btc)2-rGO/GCE修饰电极，铂电极和饱和甘汞电极为三电极体系，放入含对乙酰氨基酚和对氨基酚的磷酸缓冲溶液中（pH=8），采用差示脉冲伏安法进行扫描，扫描电位范围为-0.3~0.7V；
（3）检测结果：根据对乙酰氨基酚氧化峰电流与其浓度的线性关系、对氨基酚氧化峰电流与其浓度的线性关系，计算得到对乙酰氨基酚的浓度为200μM；对氨基酚的浓度为200μM；对乙酰氨基酚氧化峰电流与其浓度的线性关系为：Ip=0.0797c(ACOP)-23.8837；对氨基酚氧化峰电流与其浓度的线性关系为：Ip(μA)=0.0781c(4-AP)-0.7779。
Claims (9)
1.一种基于金属有机骨架的特异性修饰电极在检测水样中对乙酰氨基酚和对氨基酚浓度的应用，其特征在于：所述基于金属有机骨架的特异性修饰电极的构建方法包括以下步骤：
（1）氨基化金属有机框架材料NH2-Cu3(btc)2的制备：将均苯三酸、2-氨基对苯二甲酸充分分散于无水N,N-二甲基甲酰胺和乙醇的混合液中，再加入硝酸铜水溶液搅拌0.5~1h；然后在80~90℃下水热反应20~30小时；冷却至室温，过滤，用N,N-二甲基甲酰胺和乙醇洗涤，50~70℃下真空干燥，得到NH2-Cu3(btc)2；
（2）修饰电极rGO-NH2-Cu3(btc)2/GCE的制备：将氨基化金属有机框架NH2-Cu3(btc)2与氧化石墨烯rGO分散于N,N-二甲基甲酰胺中，形成浓度2~2.5mg/mL的分散液，再将该分散液滴涂在打磨好的玻碳电极表面，在红外灯下干燥，制得修饰电极rGO-NH2-Cu3(btc)2/GCE；
（3）特异性修饰电极Au/rGO-NH2-Cu3(btc)2/GCE的制备：以rGO-NH2-Cu3(btc)2/GCE修饰电极为工作电极，与铂电极、饱和甘汞电极组成三电极体系；插入含HAuCl4的H2SO4溶液中，采用恒电位沉积法将金纳米粒子沉积到电极表面，制得特异性修饰电极Au/rGO-NH2-Cu3(btc)2/GCE。
2.如权利要求1所述基于金属有机骨架的特异性修饰电极在检测水样中对乙酰氨基酚和对氨基酚浓度的应用，其特征在于：以Au/rGO-NH2-Cu3(btc)2/GCE修饰电极为工作电极，铂电极为对电极，饱和甘汞电极为参比电极组成三电极体系，插入含有对乙酰氨基酚和对氨基酚pH=8的磷酸缓冲溶液中，采用差示脉冲伏安法进行扫描，扫描电位范围为-0.3~0.7V；得到不同浓度的对乙酰氨基酚、对氨基酚的DPV响应，并得到不同浓度的对乙酰氨基酚、对氨基酚的响应电流与浓度的线性关系图。
3.如权利要求1所述基于金属有机骨架的特异性修饰电极在检测水样中对乙酰氨基酚和对氨基酚浓度的应用，其特征在于：在4~102μM浓度范围内，对乙酰氨基酚氧化峰电流与其浓度的线性关系为：Ip=0.3094c(ACOP)+0.1836；在102~300μM浓度范围内，对乙酰氨基酚氧化峰电流与其浓度的线性关系为：Ip=0.0797c(ACOP)-23.8837。
4.如权利要求1所述基于金属有机骨架的特异性修饰电极在检测水样中对乙酰氨基酚和对氨基酚浓度的应用，其特征在于：在4~500μM浓度范围内，对氨基酚氧化峰电流与其浓度的线性关系为：Ip=0.0781c(4-AP)-0.7779。
5.如权利要求1所述基于金属有机骨架的特异性修饰电极在检测水样中对乙酰氨基酚和对氨基酚浓度的应用，其特征在于：基于金属有机骨架的特异性修饰电极的构建方法的步骤（1）中，无水N,N-二甲基甲酰胺和乙醇的混合液中，N,N-二甲基甲酰胺与乙醇的体积比为1.5:1~1:1。
6.如权利要求1所述基于金属有机骨架的特异性修饰电极在检测水样中对乙酰氨基酚和对氨基酚浓度的应用，其特征在于：基于金属有机骨架的特异性修饰电极的构建方法的步骤（1）中，均苯三酸与2-氨基对苯二甲酸的质量比为3.5:1~3:1；均苯三酸与硝酸铜的质量比为1:0.3~1:0.5。
7.如权利要求1所述基于金属有机骨架的特异性修饰电极在检测水样中对乙酰氨基酚和对氨基酚浓度的应用，其特征在于：基于金属有机骨架的特异性修饰电极的构建方法的步骤（2）中，氨基化金属有机框架NH2-Cu3(btc)2与还原氧化石墨烯rGO的质量比为1.5:1~1:1。
8.如权利要求1所述基于金属有机骨架的特异性修饰电极在检测水样中对乙酰氨基酚和对氨基酚浓度的应用，其特征在于：基于金属有机骨架的特异性修饰电极的构建方法的步骤（3）中，H2SO4溶液的浓度为0.1~0.15M；HAuCl4的浓度为2~2.5mM。
9.如权利要求1所述基于金属有机骨架的特异性修饰电极在检测水样中对乙酰氨基酚和对氨基酚浓度的应用，其特征在于：基于金属有机骨架的特异性修饰电极的构建方法的步骤（3）中，恒电位沉积的条件为：沉积电位范围为-0.4~0.1V，沉积时间为60~100s。
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