CN105842307A - 一种高灵敏度酚类电化学传感器及其制备方法 - Google Patents
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Abstract
本发明公开了一种高灵敏度酚类电化学传感器及其制备方法,其步骤为:将制备的多壁碳纳米管桥联的3D石墨烯导电网络超声分散于水中,并滴涂于已抛光的玻碳电极上并干燥,制得所述的传感器。该3D功能化纳米材料构建的纳米传感器可以在其他干扰物质存在的复杂环境下,实现对氨基苯酚、对氯苯酚和对硝基苯酚等的电化学检测,有效解决了CDs易脱落的缺陷,羧基化碳纳米管的非共价桥联将显著提高体系的导电性及CDs的选择性,本发明方法更加经济,可行性更好,灵敏度更高。
Description
技术领域
本发明涉及一种高灵敏度酚类电化学传感器及其制备方法,特别是一种具有对对氨基苯酚(4-AP)、对氯苯酚(4-CP)和对硝基苯酚(4-NP)等电化学增强响应的电化学传感器及其制备方法。
背景技术
酚类化合物是一种很重要的化工原料,也是化学工业中的副产物。它们被广泛应用于工业制品中,可以在环境或通过野生动物消耗或植物摄取的生态食物链中蓄积。这些化合物具有极高的毒性,又很难被生物及非生物降解,因此,它们对环境和人类健康有着显著的毒性风险。特别地,对氨基苯酚(4-AP)、对氯苯酚(4-CP)和对硝基苯酚(4-NP)化合物是其中的主要污染物,被美国环境保护局和欧洲联盟等国际机构监视。酚类化合物的应用代表了污染的潜在来源,影响包括藻类和水生种子植物的水生生物。这些有毒的酚衍生物释放到环境中,其检测和定量分析对监测评价环境样品的总体毒性极为重要。
近年来,电化学感测技术因具有简单、快速、选择性好、成本低、易于小型化,以及在线监测能力等众多优点,在苯酚化合物的检测上受到了极大关注。电化学传感器的性能和表面特性是高度相关的,发展电化学感测的关键策略是控制电极界面的结构。有机、无机、金属、聚合物和生物分子已经被用于修饰传感电极来提高灵敏度和选择性。碳材料由于其优异的稳定性,宽电位窗,良好的电子传输能力,受到了研究者的关注。其中,石墨烯凭借化学耐受性、比表面积大以及导电性已经成为基础科学和技术领域里的迷人材料,并具有更大的表面积、高导电性和载流子浓度和迁移率。石墨烯与碳纳米管的协同组合将获得比任一单独组分更加优异的性能。多壁碳纳米管桥联的3D石墨烯导电网络已经成功制备,(我们已申请中国发明专利,申请号:201510053820.1)并可成功应用于多巴胺(3,4-二羟苯基乙胺,DA),抗坏血酸(AA),尿酸(UA)和色氨酸(Trp)的电化学灵敏检测。对于早期临床诊断和神经化学研究领域里生理选择性电化学的检测和量化起到了重要作用。
在过去的几年中,对4-AP、4- CP、4-NP的检测虽然获得了满意的结果,但是
常用到的主体物质如环糊精(CDs)及其衍生物是非导电的,不利于电子的传输;贵金属虽导电性好,却存在价格高昂等缺陷。作为一个最广泛研究的主体,CDs,可以和多种有机、无机和生物客体分子相互作用,能形成稳定的主客体配合物,只要它们具有充分适当的极性和大小即可形成配合物。
发明内容
本发明针对现有技术中存在操作繁琐、步骤繁多、检测灵敏度低等不足提供了一种高灵敏度酚类电化学传感器及其制备方法。
实现本发明目的的技术解决方案为:一种高灵敏度酚类电化学传感器,利用多壁碳纳米管桥联的3D石墨烯导电网络为活性材料,将其超声分散于溶剂中,并滴涂于玻碳电极的表面构建成所述的传感器,其中,所述的多壁碳纳米管桥联的3D石墨烯导电网络具有如下结构:
。
一种高灵敏度酚类电化学传感器的制备方法,其具体的工艺包括以下步骤:
步骤1、构建多壁碳纳米管桥联的3D石墨烯导电网络作为活性材料;
步骤2、将活性材料超声分散于溶剂中制得滴涂液;
步骤3、抛光玻碳电极;
步骤4、将步骤2的滴涂液涂覆于步骤3中的电极表面后,滴涂0.1~3 μL 全氟磺酸-聚四氟乙烯共聚物(Nafion)以提高电极稳定性;
步骤5、干燥后即得到电化学传感器。
进一步的,步骤1中,所述的多壁碳纳米管桥联的3D石墨烯导电网络由如下步骤制备:
第一步、以天然鳞片石墨粉制备氧化石墨固体;
第二步、超声制备氧化石墨烯DMF悬浮液;
第三步、制备CDs功能化的氧化石墨烯GO-CDs;
第四步、分别制备GO-CDs的DMF悬浮液和羧基化的碳纳米管的DMF悬浮液;
第五步、将第四步的两种悬浮液混合后,加入还原剂于50~80 ℃下搅拌反应;
第六步、减压过滤、洗涤、干燥后即得到多壁碳纳米管桥联的3D石墨烯导电网络。
进一步的,步骤2中,所述的超声制备活性材料滴涂液的溶剂为水和全氟磺酸-聚四氟乙烯共聚物的共混溶剂,所述的全氟磺酸-聚四氟乙烯共聚物浓度为0.5 wt%;共混溶剂的体积比为1:1 ~ 9:1; 活性材料与溶剂的比例为(1:5 ~ 5:1)mg/mL;超声时间为1~10h。
进一步的,步骤4中,全氟磺酸-聚四氟乙烯共聚物的浓度为0.5 wt%。
与现有技术相比,本发明具有以下优点:
(1)构建3D的导电网络因其具有独特的三维结构,可有效加快响应时间,提高电催化检测性。且合成步骤简单,高效,灵敏,在环境检测领域里具有重要的推广、应用价值。构建方法贴近绿色化学的要求,且操作简单,易于控制,有利于实际应用。
(2) 对于典型污染物4-AP、4- CP、4-NP等具有极高的检测灵敏度,且响应时间短,适合微量污染物的监测与分析。
下面结合附图对本发明的实施例作进一步详细说明。
附图说明
图1是本发明制备的高灵敏度酚类电化学传感器制备过程示意图。
图2是本发明实施例1中构建的高灵敏度酚类电化学传感器对4-AP的循环伏安曲线,其中,a, GCE; b, GO-CDs; c, GN-CDs; d, GN-CDs-MWNTs。
图3是本发明实施例1中构建的高灵敏度酚类电化学传感器对4-CP的循环伏安曲线,其中,a, GCE; b, GO-CDs; c, GN-CDs; d, GN-CDs-MWNTs。
图4是本发明实施例1中构建的高灵敏度酚类电化学传感器对4-CP的差分脉冲伏安曲线,其中,Ipa1=4.506 +0.294CCP (μA, μM, R=0.998), Ipa2=7.237+0.034CCP (μA, μM,R=0.996),检测限为0.0169 μM。
具体实施方式
下面结合附图对本发明的实施例作进一步详细说明,本实施例在以本发明技术方案前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
如图1所示,一种高灵敏度酚类电化学传感器的构建方法,该方法包括以下步骤:
步骤1、构建多壁碳纳米管桥联的3D石墨烯导电网络;可参照已申请的中国发明专利(申请号:201510053820.1)进行制备。
步骤2中所述的超声制备活性材料滴涂液的溶剂为水和全氟磺酸-聚四氟乙烯共聚物的共混溶剂,所述的Nafion浓度为0.5 wt%;共混溶剂的体积比为1:1 ~ 9:1; 活性材料与溶剂的比例为(1:5 ~ 5:1)mg/mL;超声时间为1~10 h。
步骤3、抛光玻碳电极;
步骤4、将步骤2的滴涂液涂覆于步骤3中的电极表面;干燥后,需再次滴涂0.1~3 μLNafion以提高电极稳定性。
步骤5、干燥后即得到电化学传感器;
步骤6、利用电化学测试技术进行检测。
实施例1
第一步,多壁碳纳米管桥联的3D石墨烯导电网络的制备;
在80 ℃,用30 mL 浓硫酸、10 g 过硫酸钾和10 g 五氧化二磷将20 g天然石墨预氧化后,水洗至pH=7,常温干燥过夜待用;将460 mL浓硫酸冷却到0 ℃左右,然后将20 g预氧化的石墨加入到其中,慢慢加入60 g高锰酸钾,使得体系温度不超过20 ℃,添加完毕后升温到35 ℃,搅拌2 h以后,并分批慢慢加入920 mL去离子水,使得体系温度不超过98 ℃,再搅拌15分钟以后,加入2.8 L去离子水和50 mL 30 % 双氧水。将得到的亮黄色悬浮液减压抽滤,洗涤。一直到滤液中没有硫酸根离子,且呈中性时,将产物在60 ℃真空中烘干,得到氧化石墨固体;
将200 mg氧化石墨粉末装入圆底烧瓶,再加入15 mL N, N-二甲基甲酰胺(DMF)溶剂,超声5 h后,得到氧化石墨烯的悬浮液;加入40 mL二氯亚砜(SOCl2),在70 ℃下反应24 h后,减压蒸馏以除去多余的SOCl2,最后加入溶于22 mL DMF的4 g β-CDs, 90℃下油浴反应2天,得到GO-CDs。
将20 mg第二步产物GO-CDs和20 mg羧基化MWNTs分别超声5 h分散于20 mL N,N-二甲基甲酰胺(DMF)里。然后将良好分散的两种悬浮液混合后,加入600 μL氨水和50 μL水合肼,60 ℃搅拌反应3.5 h。得到的粗产物经抽滤,洗涤,干燥后,即得产物。
第二步、将2 mg第一步的产物超声分散于水和全氟磺酸-聚四氟乙烯共聚物的共混溶剂中,两种溶剂的体积比为9:1; 活性材料与溶剂的比例为1:1 mg/mL;超声时间为10h。
第三步、抛光玻碳电极;
第四步、将步骤2的滴涂液涂覆于步骤3中的电极表面;干燥后,需再次滴涂2 μLNafion以提高电极稳定性,经试验发现,如果不额外滴涂Nafion溶液,在测试过程中,纳米材料极易容易从玻碳电极表面脱落,造成无法检测的情况。因此,本发明中特别强调需要额外滴涂以保证测试效果。
第五步、干燥后即得到电化学传感器;
第六步、利用电化学测试技术进行检测,其检测结果如图2-4所示。图2,3分别为构建的高灵敏度酚类电化学传感器对4-AP,4-CP的循环伏安曲线。结果说明,CD的引入将增强电化学活性;GO-CD还原为GN-CD后,由于恢复了石墨烯部分导电性,所以电催化活性得到进一步增强;引入MWNTs以后,传感材料体系(GN-CD-MWNTs)导电性显著增大,进而达到了最大的电催化活性。该方法对4-AP, 4-CP及4-NP均具有相似催化性能。
图4是本发明实施例1中构建的高灵敏度酚类电化学传感器对4-CP的差分脉冲伏安曲线,经研究表明,最优化结构的传感材料GN-CD-MWNTs对4-CP的检测存在2个线性范围,Ipa1=4.506 +0.294CCP (μA, μM, R=0.998), Ipa2=7.237+0.034CCP (μA, μM, R=0.996),检测限可达到0.0169 μM。这些结果证明,本发明可以应用于酚类物质的电化学检测与分析。
实施例2
第一步,同实施例1中的步骤一;
第二步,将2 mg第一步的产物超声分散于水和全氟磺酸-聚四氟乙烯共聚物的共混溶剂中,Nafion的浓度为0.5 wt%,的共混溶剂中,两种溶剂的体积比为1:1; 活性材料与溶剂的比例为1:5 mg/mL;超声时间为1 h。
第三至六步,同实施例1中的步骤三至六。
实施例3
第一步,同实施例1中的步骤一;
第二步,将2 mg第一步的产物超声分散于水和全氟磺酸-聚四氟乙烯共聚物的共混溶剂中,Nafion的浓度为0.5 wt%,两种溶剂的体积比为5:1; 活性材料与溶剂的比例为5:1mg/mL;超声时间为5 h。
第三至六步,同实施例1中的步骤三至六。
实施例4
第一步,同实施例1中的步骤一;
第二步,将2 mg第一步的产物超声分散于水和全氟磺酸-聚四氟乙烯共聚物的共混溶剂中,Nafion的浓度为0.5 wt%,两种溶剂的体积比为1:3; 活性材料与溶剂的比例为1:1mg/mL;超声时间为7 h。
第三至六步,同实施例1中的步骤三至六。
实施例5
第一至三步,同实施例1中的步骤一至三;
第四步,将步骤2的滴涂液涂覆于步骤3中的电极表面;干燥后,需再次滴涂3 μLNafion以提高电极稳定性。
第五至六步,同实施例1中的步骤五至六。
实施例6
第一至三步,同实施例1中的步骤一至三;
第四步,将步骤2的滴涂液涂覆于步骤3中的电极表面;干燥后,需再次滴涂0.1 μLNafion以提高电极稳定性。
第五至六步,同实施例1中的步骤五至六。
Claims (6)
1.一种高灵敏度酚类电化学传感器,其特征在于,利用多壁碳纳米管桥联的3D石墨烯导电网络为活性材料,将其超声分散于溶剂中,并滴涂于玻碳电极的表面构建成所述的传感器, 其中,所述的多壁碳纳米管桥联的3D石墨烯导电网络具有如下结构:
。
2.一种高灵敏度酚类电化学传感器的制备方法,其特征在于,具体包括以下步骤:
步骤1、构建多壁碳纳米管桥联的3D石墨烯导电网络作为活性材料;
步骤2、将活性材料超声分散于溶剂中制得滴涂液;
步骤3、抛光玻碳电极;
步骤4、将步骤2的滴涂液涂覆于步骤3中的电极表面后,滴涂0.1~3 μL 全氟磺酸-聚四氟乙烯共聚物;
步骤5、干燥后即得到电化学传感器。
3.如权利要求2所述的高灵敏度酚类电化学传感器的制备方法,其特征在于,步骤1中,所述的多壁碳纳米管桥联的3D石墨烯导电网络由如下步骤制备:
第一步、以天然鳞片石墨粉制备氧化石墨固体;
第二步、超声制备氧化石墨烯DMF悬浮液;
第三步、制备CDs功能化的氧化石墨烯GO-CDs;
第四步、分别制备GO-CDs的DMF悬浮液和羧基化的碳纳米管的DMF悬浮液;
第五步、将第四步的两种悬浮液混合后,加入还原剂于50~80 ℃下搅拌反应;
第六步、减压过滤、洗涤、干燥后即得到多壁碳纳米管桥联的3D石墨烯导电网络。
4.如权利要求2所述的高灵敏度酚类电化学传感器的制备方法,其特征在于,步骤2中,所述的超声制备活性材料滴涂液的溶剂为水和全氟磺酸-聚四氟乙烯共聚物的共混溶剂;共混溶剂的体积比为1:1 ~ 9:1; 活性材料与溶剂的比例为(1:5 ~ 5:1)mg/mL;超声时间为1~10 h。
5.如权利要求4所述的高灵敏度酚类电化学传感器的制备方法,其特征在于,全氟磺酸-聚四氟乙烯共聚物浓度为0.5 wt%。
6.如权利要求2所述的高灵敏度酚类电化学传感器的制备方法,其特征在于,步骤4中,全氟磺酸-聚四氟乙烯共聚物的浓度为0.5 wt%。
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