CN107643331A - 一种电极表面修饰材料及其制备方法和应用 - Google Patents
一种电极表面修饰材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种电极表面修饰材料及其制备方法和应用，具体是一种巯基‑β‑环糊精功能化石墨烯负载铜纳米微球(HS‑β‑CD‑RGO/CuNSs)分散于水中形成的一种混悬液及其制备方法。上述混悬液滴涂于常规的洁净的电极表面，置于红外灯下烤干后，可得到高灵敏对硝基苯酚电化学传感器，可用于对硝基苯酚检测。本发明中纳米复合材料的制备方法简单快捷，成本低，稳定性好，制备的电化学传感器响应迅速、灵敏度高、线性范围宽、重现性好。有望在水中对硝基苯酚的检测和环境监测等领域得到广泛的应用。
Description
技术领域
本发明涉及电极表面修饰材料，尤其涉及一种用于电化学检测对硝基苯酚的电极表面修饰材料及其制备方法和应用。
背景技术
对硝基苯酚(4-nitrophenol，4-NP)是极具毒性的酚类化合物，由于其对人类和动植物的生长和代谢具有广泛的危害性，已经被美国国家环境保护局列为优先级有毒污染物。低浓度的对硝基苯酚就可产生对眼睛、皮肤和呼吸道的刺激，并引起头痛、恶心、紫绀等症状。对硝基苯酚的定量分析和检测对人类健康与环境保护具有十分重要的意义。传统检测方法主要包括高效液相色谱法、毛细管电泳法、化学发光法、荧光法和光谱法等，但这些方法通常操作复杂、仪器昂贵，难于实现实时的现场检测。而电化学方法具有操作简便、仪器相对便宜和易于实现现场检测等优点，因此，发展对硝基苯酚电化学传感器成为研究的热点。然而，未经修饰的玻碳电极却表现出灵敏度低、电极反应速度慢等缺陷。所以，寻找合适的材料对玻碳电极进行修饰，成为构建高灵敏的对硝基苯酚电化学传感器的关键。近年来，随着纳米科技的发展，越来越多的纳米材料包括：Au、Pd、Pt、Ag等贵金属及其合金纳米粒子和碳纳米管、石墨烯等电极基底材料被应用到电化学传感器中，使对硝基苯酚电化学信号得到有效放大，取得了良好的检测效果。但Au、Pd、Pt、Ag等贵金属成本高且稀有，如果找到成本低廉、储量丰富的非贵金属来替代贵金属，将会使传感器的生产成本和使用成本大大降低，有助于该电化学传感器广泛应用。最近的研究表明，铜纳米材料对对硝基苯酚具有良好的催化还原活性。因此，本发明合成了巯基-β-环糊精功能化石墨烯负载铜纳米微球纳米复合材料，将其修饰于玻碳电极表面，构建了对硝基苯酚电化学传感器，实现了对硝基苯酚快速、灵敏、高效的电化学检测。
发明内容
本发明的目的在于提供一种用于电化学检测对硝基苯酚的电极表面修饰材料及其制备方法和应用；所述修饰材料制备工艺简单，成本低廉；用于电化学检测对硝基苯酚灵敏度高。
本发明提供的一种用于电化学检测对硝基苯酚的电极表面修饰材料，通过如下步骤的方法制得：
1)巯基-β-环糊精功能化石墨烯(HS-β-CD-RGO)的制备：
将巯基-β-环糊精、氧化石墨烯加入二次水中，加入氨水后搅拌5-20min，搅拌状态下加入水合肼，所述的氧化石墨烯、巯基-β-环糊精、氨水、水合肼和二次水的质量比为1:6-10:0.2-0.3:0.006-0.01:2500-3500(优选1:8:0.24:0.008:3000)，置于40-80℃(优选60℃)水浴中搅拌反应2-4小时(优选3.5小时)；
室温下，11000-13000rpm，离心15-25min，弃上清，加入二次水得到浓度为1.0mg/mL的HS-β-CD-RGO黑色混悬液；
2)HS-β-CD-RGO负载铜纳米微球(HS-β-CD-RGO/CuNSs)复合物的制备：
室温下，将步骤1)制得的HS-β-CD-RGO黑色混悬液，加入二次水、五水硫酸铜，冰浴搅拌5-20min之后，在冰浴搅拌状态下缓慢加入新配制的硼氢化钠，所述的HS-β-CD-RGO、五水硫酸铜、硼氢化钠和二次水的质量比为1:1-1.5:1.3-1.9:5000-7000(优选1:1.25:1.52:6000)，在氮气保护条件下，继续搅拌反应2.5-3.5小时(优选3小时)，4℃静置24小时，5000-7000rpm，离心8-12min，弃上清，加入二次水得到稳定的HS-β-CD-RGO/CuNSs混悬液。
本发明提供的一种用于电化学检测对硝基苯酚的电极，其表面修饰有步骤2)得到的HS-β-CD-RGO/CuNSs复合物。所述的电极为玻碳电极。
与现有技术相比，本发明的HS-β-CD-RGO/CuNSs复合材料可用于对硝基苯酚的电化学分析检测，检测时间短、灵敏度高，线性范围宽，重现性好，成本低廉，制备过程在常温常压下进行，方法简单可行。
附图说明
图1本发明制备的HS-β-CD-RGO/CuNSs的透射电子显微镜图。
图2本发明制备的HS-β-CD-RGO/CuNSs的傅里叶变换红外光谱图。
图3本发明制备的HS-β-CD-RGO/CuNSs修饰的玻碳电极在不同浓度对硝基苯酚溶液中线性伏安扫描图。
图4本发明制备的HS-β-CD-RGO/CuNSs修饰的玻碳电极检测对硝基苯酚的标准曲线图。
具体实施方式
实施例1 电极表面修饰材料HS-β-CD-RGO/CuNSs混悬液的制备及对硝基苯酚的测定。
1.巯基-β-环糊精功能化石墨烯(HS-β-CD-RGO)的制备：
(1)将4.0mg/mL巯基-β-环糊精水溶液5.0mL加入2.5mL的1.0mg/mL氧化石墨烯混悬液中，再加入25％的氨水600μL，搅拌20min之后，搅拌状态下加入80％水合肼40μL，置于60℃水浴中搅拌反应3.5小时。
(2)室温下，12000rpm，离心20min，弃上清，加入2.5mL二次水得到1.0mg/mL的巯基-β-环糊精功能化石墨烯(HS-β-CD-RGO)，为黑色混悬液。
2.HS-β-CD-RGO负载铜纳米微球(HS-β-CD-RGO/CuNSs)复合物的制备：
室温下，步骤1制得的HS-β-CD-RGO 1.0mL，加入3.0mL二次水中，再加入25mmol/L五水硫酸铜溶液200μL，冰浴搅拌20min之后，在冰浴搅拌状态下缓慢加入新配制的浓度为20mmol/L硼氢化钠溶液2.0mL，在氮气保护条件下继续搅拌反应3小时，4℃静置24小时。6000rpm，离心10min，弃上清，加入2.0mL二次水得到0.5mg/mL的稳定的黑色HS-β-CD-RGO/CuNSs混悬液(见图1和图2)。此混悬液可用于玻碳电极表面修饰。
3.取上述得到的HS-β-CD-RGO/CuNSs混悬液6μL滴涂于干净的玻碳电极表面，置于红外灯下烤干，冷却至室温，得到HS-β-CD-RGO/CuNSs复合物修饰的玻碳电极。
4.将所制备的玻碳电极作为工作电极，饱和甘汞电极作为参比电极，铂电极作为辅助电极，同时连接电化学工作站，并将电极浸入5mL的磷酸缓冲溶液(0.1mol/L，pH 2.0)中，加入不同浓度的对硝基苯酚溶液，搅拌富集3min，用线性扫描伏安法检测，电位范围为0～-1.0V，扫速为0.1V/s，记录峰电流变化，结果见图3和图4。测试对硝基苯酚的浓度范围为0.05至100μmol/L。
本发明HS-β-CD-RGO/CuNSs复合物检测速度快、灵敏度高，检测限低(20nM)，线性范围宽，重现性好，成本低廉，而且制备方法简单。与金、银、碳纳米管等同类型复合材料相比，其性能有很大提高(见表1)，具有非常好的应用前景。
表1 各种对硝基苯酚传感材料性能比较
Claims (9)
1.一种用于电化学检测对硝基苯酚的电极表面修饰材料，其特征在于，通过包括如下步骤的方法制得：
1)巯基-β-环糊精功能化石墨烯(HS-β-CD-RGO)的制备：
将巯基-β-环糊精、氧化石墨烯加入二次水中，加入氨水后搅拌5-20min，搅拌状态下加入水合肼，所述的氧化石墨烯、巯基-β-环糊精、氨水、水合肼和二次水的质量比为1:6-10:0.2-0.3:0.006-0.01:2500-3500，置于40-80℃水浴中搅拌反应2-4小时；
室温下，11000-13000rpm，离心15-25min，弃上清，加入二次水得到浓度为1.0mg/mL的HS-β-CD-RGO黑色混悬液；
2)HS-β-CD-RGO负载铜纳米微球(HS-β-CD-RGO/CuNSs)复合物的制备：
室温下，将步骤1)制得的HS-β-CD-RGO黑色混悬液，加入二次水、五水硫酸铜，冰浴搅拌5-20min之后，在冰浴搅拌状态下缓慢加入新配制的硼氢化钠，所述的HS-β-CD-RGO、五水硫酸铜、硼氢化钠和二次水的质量比为1:1-1.5:1.3-1.9:5000-7000，在氮气保护条件下，继续搅拌反应2.5-3.5小时，4℃静置24小时，5000-7000rpm，离心8-12min，弃上清，加入二次水得到稳定的HS-β-CD-RGO/CuNSs混悬液。
2.如权利要求1所述的电极表面修饰材料，其特征在于，所述步骤1)中氧化石墨烯、巯基-β-环糊精、氨水、水合肼和二次水的质量比为1:8:0.24:0.008:3000。
3.如权利要求1所述的电极表面修饰材料，其特征在于，所述步骤1)中水浴温度为60℃。
4.如权利要求1所述的电极表面修饰材料，其特征在于，所述步骤1)中反应时间为3.5小时。
5.如权利要求1所述的电极表面修饰材料，其特征在于，所述步骤2)中的HS-β-CD-RGO、五水硫酸铜、硼氢化钠和二次水的质量比为1:1.25:1.52:6000。
6.如权利要求1所述的电极表面修饰材料，其特征在于，所述步骤2)中反应时间为3小时。
7.一种电化学检测对硝基苯酚的电极，其特征在于，所述电极表面修饰有如权利要求1所述的修饰材料。
8.如权利要求7所述的一种电化学检测对硝基苯酚的电极，其特征在于，所述的电极为玻碳电极。
9.如权利要求1-6所述的任一种电极表面修饰材料在电化学检测对硝基苯酚中的应用。
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