CN115165989A - 一种电化学柔性传感芯片及其应用 - Google Patents
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Abstract
本发明属于环境污染物传感技术领域,具体涉及一种单原子钴(SA‑Co)材料及其制备和应用。所述单原子钴材料的的制备方法,包括以下步骤:以三聚氰胺、氨基酸和醋酸钴为前驱体,控制前驱体的比例,球磨混匀,高温裂解,得到所述单原子钴材料。本发明制备得到单原子钴,将其用于构建电化学柔性传感芯片,能够同时检测三种苯二酚异构体;此外,该传感器具备良好的重现性、稳定性以及选择性,对其他离子具有良好的抗干扰性。
Description
技术领域
本发明属于环境污染物传感技术领域,具体涉及一种单原子钴材料及其制 备和应用。
背景技术
苯二酚是一种典型的酚类污染物,包括对苯二酚(HQ)、邻苯二酚(CC)和 间苯二酚(RS)三种同分异构体,它们作为中间产品被广泛用于有机合成、染料、 农药、化妆品和医药等领域。苯二酚具有高毒性、致癌性和难降解性,对环境 危害极大,亦对人体健康构成严重威胁。美国环境保护总署(EPA)和欧盟已将苯 二酚异构体列为优先污染物。然而苯二酚异构体三者在结构和理化性质上十分 相似,且常在水中共存。构建简单快速灵敏的检测方法实现三种苯二酚异构体 的检测十分迫切。目前,检测苯二酚异构体的方法有分光光度法、同步荧光法、 高效液相色谱法以及电化学法。与其他方法相比,电化学法因其价格低,灵敏度高,操作简单,选择性好,已经成为最有发展前途和最有效的一种方法。
现有技术中,如申请号为2012105879641的中国专利公开了一种金/钴氢氧 化物膜修饰玻碳电极在酚类物质检测中的应用,采用金/钴氢氧化物膜修饰玻碳 电极,对邻苯二酚和对苯二酚具有较高的电催化能力,但是并没有提及间苯二 酚,同时检出限还处于较高水平。
发明内容
本发明旨在提供一种电化学柔性传感芯片及其应用,采用单原子钴材料构 建电化学柔性传感芯片,灵敏度高,催化性能好,能够同时检测苯二酚三种异 构体,检测限低。
按照本发明的技术方案,所述电化学柔性传感芯片,包括工作电极、参比 电极和对电极(辅助电极),所述工作电极包含单原子钴材料,所述单原子钴 材料的制备方法如下,
S1:以三聚氰胺(C3H6N6)、氨基酸和含钴化合物为前驱体,球磨混匀, 得到混合物;
S2:对所述混合物进行热解,得到所述单原子钴材料(SA-Co)。
进一步的,所述工作电极为柔性工作电极,由SA-Co为墨水,打印在导电 基底上制备得到。
具体的,将SA-Co溶解于有机溶剂(如N-甲基吡咯烷酮),配制成10mg/mL 的溶液,再加入0.2wt%的壳聚糖调整粘稠度,得到墨水,再采用高分辨直流体 打印技术,将所述墨水打印在碳基底上,制备得到柔性工作电极;所述碳基底、 参比电极和对电极可以由导电碳浆打印得到。
进一步的,所述氨基酸为丙氨酸、半胱氨酸或络氨酸等氨基酸小分子。
进一步的,所述含钴化合物为二氯化钴或醋酸钴。
进一步的,所述三聚氰胺、氨基酸和含钴化合物的质量比为40-10000: 20-100:1
具体的,所述三聚氰胺与氨基酸的质量比为2-100:1,所述氨基酸与含钴 化合物的质量比为20-100:1。
优选的,所述含钴化合物为醋酸钴,所述氨基酸为丙氨酸;丙氨酸与醋酸 钴的质量比为40:1(在一个实施例中,丙氨酸与醋酸钴的用量分别为2.0g和 0.05g);三聚氰胺与丙氨酸的质量比为5:1。
进一步的,所述步骤S2中,热解的温度为600-900℃,时间为1.5-4h;优 选的,热解温度为500℃,时间为2h。
进一步的,热解在保护气氛下进行,如氮气、氩气等,升温速率为2-4℃/min, 优选为2.5℃/min。
上述电化学柔性传感芯片具有良好的选择性,便于苯二酚检测,因此本发 明的第二方面提供了上述电化学柔性传感芯片在苯二酚检测中的应用。
进一步的,用于判断苯二酚异构体的类型。
本发明的第三方面提供了一种苯二酚检测的方法,将上述的电化学柔性传 感芯片置于含苯二酚的检测液中,检测电化学信号,同时可以评价传感器对苯 二酚的选择性响应性能,从而判断苯二酚异构体的类型。
进一步的,所述检测液的pH值为5-8,优选为6.5。
具体的,所述检测液可以以磷酸盐缓冲溶液(PBS)溶液为底液。
本发明的技术方案相比现有技术具有以下优点:本发明以SA-Co构建电化 学柔性传感芯片,能够同时检测苯二酚三种异构体;此外,该传感器具备良好 的重现性、稳定性以及选择性,对其他的离子具有良好的抗干扰性。
附图说明
图1为(a)电化学柔性芯片的构建图;(b)SA-Co的SEM图;(c)SA-Co的TEM 图;(d)SA-Co的HAAD-STEM图像;(e)SA-Co的EDX元素映射谱。
图2为(a)SA-Co、GO和NG对0.5M PBS、0.5mM HQ、0.5mM CC、0.5mM RS的DPV响应曲线;(b)响应电流的比较;(c)SA-Co对PBS、0.5mM HQ、 0.5mM CC、0.5mM RS和0.5mM HQ、CC和RS混合物的DPV响应曲线; (d)SA-Co对HQ、CC和RS的PH优化;(e)Logν和log IP关系图;(f)SA-Co材料修饰量的优化;(g-i)SA-Co分别对HQ、CC和RS的电位优化。
图3为(a-d)SA-Co对不同浓度HQ、CC和RS的DPV响应曲线;(e-f)SA-Co 传感器对HQ、CC、RS的抗干扰性能。
图4为XPS图(a)C 1s窄谱图;(b)N 1s窄谱图;(c)Co 2p窄谱图。
图5为SA-Co传感器分别在+0.06V、+0.140V和+0.56V下对(a)HQ、(b)CC 和(c)RS的电流-时间曲线;(d-f)-分别为HQ、CC和RS的线性回归曲线。
图6为电化学柔性传感器芯片在纺织废水中的检测图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明,以使本领域的技术人 员可以更好地理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
实施例1:合成SA-Co
SA-Co单原子催化剂是将C3H6N6(12g)、C3H7NO2(2g)和 Co(CH3COO)2·4H2O(0.05g)球磨混合,然后放入管式炉中制成。在氮气气氛中, 升温速率为2.5℃min-1,600℃保温2h后,以5℃min-1速率升至900℃并保持 1.5h,最后,在氮气保护下将材料自然冷却至室温。
将上述Co(CH3COO)2·4H2O替换为二氯化钴,同样可以进行反应。
实施例2:电化学检测
电化学性能在电化学工作站(CHI660E)上进行测试。以SA-Co修饰的导电碳 浆为工作电极,以饱和氯化银(AgCl)为参比电极,以碳浆直接作为辅助电极, 三者共同构成三电极体系。并以磷酸盐缓冲溶液(PBS)作为电解质溶液,再借助 于电化学工作站的DPV(差分脉冲伏安法)方法对一定浓度下的HQ、CC和 RS进行电化学性能测试。
测试例
1、复合材料的结构形貌表征
图1是检测原理示意图。单原子SA-Co催化剂是通过在氮气保护下裂解三 聚氰胺、丙氨酸和醋酸钴来制备的(图1a)。图1b和1c表明SA-Co呈现出具 有光滑表面的片状结构。元素映射测量(EDX)表明C、N、Co均匀分布在样品中, (图2e)。球差校正透射电子显微镜(HAAD-STEM)图像突出了分散在单原 子材料载体上的高密度亮点(图1d)。
2、XPS用于研究单原子催化剂的化学状态和元素组成。
Co 2p3/2在SA-Co中的结合能为780.51eV,Co 2p1/2在SA-Co中的结合 能为796.01eV(图4c)。对C1s窄谱进行分析,可将其拟合成sp2 C(284.60eV)、 sp3 C/C-N(285.17eV)、C-2N/C-O(286.05eV)和-COOH(288.79eV)四 种构型(图4a)。为了研究N掺杂引起材料组成变化,本发明进一步地将N1s XPS谱图进行解析,位于398.42、399.46、400.93和402.39eV的谱峰分别对应 吡啶氮、吡咯氮、季铵盐氮和N-O四种氮构型(图4b)。
3、SA-Co单原子柔性传感芯片对苯二酚的检测
将SA-Co材料用于苯二酚电化学传感器的构建,并对苯二分异构体分子的 电化学行为进行研究。采用DPV技术测试SA-Co、GO和NG在0.5M PBS(pH 6.5)中对0.5mM HQ、0.5mMCC和0.5mM RS的电化学响应(图2a-c)。SA-Co 传感平台对0.5mM HQ、0.5mM CC和0.5mM RS的电化学响应呈现各自独立 的氧化峰,其峰电位(Ep)分别为+0.04V、+0.14V和+0.56V,而对三者的混 合物的峰电位与单独的苯二酚异构体一致且未出现峰位交叠。NG传感平台对0.5mM HQ、0.5mM CC和0.5mM RS的电化学响应呈现各自独立的氧化峰, 其峰电位(Ep)分别为+0.04V、+0.14V和+0.56V,而对三者的混合物的峰电 位与单独的苯二酚异构体一致且未出现峰位交叠。但是其对HQ、CC的响应明 显低于SA-Co。GO传感平台对0.5mM HQ、0.5mM CC和0.5mM RS的电化 学响应没有呈现各自独立的氧化峰,出现了峰位交叠。表明GO传感平台不能 很好的区分HQ和CC。而且,当三种异构体同时存在且浓度不断变化时,SA-Co 传感平台仍能同时识别和检测不同浓度的HQ、CC和RS。因此,SA-Co传感平 台鉴别HQ、CC和RS分子是十分可行的,因为三者的氧化峰电位没有发生重 叠且响应很好。进一步采用DPV技术对检测体系的pH值进行优化(图2d)。 发现随着pH增大,HQ、CC及RS的氧化电位随之发生负移。尽管电位越负越 有利于氧化反应的发生,但苯二酚异构体在中性至碱性易发生严重的自氧化过 程,因此选择pH为6.5的PBS作为检测体系的支持电解质。另外,在不同扫速 下对0.1mM HQ、0.1mM CC和0.1mM RS进行CV测试,并通过研究logν和 log ip的关系可知HQ和CC是受扩散和表面协同控制的,而RS属于扩散控制 (图2e)。此外,对电极上SA-Co材料的修饰量进行优化,通过三种异构体的 DPV响应可判断修饰量为8μL,三者的氧化反应达到最佳(图2f)。另外,利 用电流-时间曲线法对HQ、CC和RS的施加电位进行调控,发现HQ和CC分 别在+0.06V和+0.140V电化学氧化反应灵敏度最高。而RS由于电化学不可逆的 原因,因而选择+0.56V作为最佳电位,因为在此电位下响应最为稳定(图2g-i)。 用DPV技术进行了测试,发现SA-Co传感平台在三种异构体同时存在且浓度不 断变化的情况下,仍然可以同时识别和检测不同浓度的HQ、CC和RS。并且它 们的响应电流与浓度具有一定的线性关系(图3a-d)。研究了SA-Co传感器在 检测HQ、CC和RS对水环境中无机离子等常见酚类物质的抗干扰能力(图3e-f)。 发现10倍量的Ca2+、Cu2+、Co2+、Ni2+、Zn2+、Ac-(CH3COO-)、SO4 2-和NO3-以及100倍量的K+、Na+、NH4+和Cl-不干扰测定98μM HQ、98μM CC和 98μM RS。此外,10倍苯酚、邻硝基苯酚(o-NP)、对硝基苯酚(p-NP)和对氯 苯酚(p-CP)对98μM HQ和98μM CC的检测没有影响。因此,SA-Co对HQ、 CC和RS具有良好的抗干扰能力,进一步说明了同时测定苯二醇异构体中SA-Co 的可行性和实用性。使用计时电流法定量测定+0.06V、+0.140V和+0.56V的 HQ、CC和RS分子(图5a~c)。HQ、CC和RS的线性回归方程(图5d~f)由 苯二醇异构体浓度与相应响应电流ΔI的关系得出,ΔI(mA)=0.00509c(HQ) (mM)+0.000415(R2=0.988)和ΔI(mA)=0.00243c(HQ)(mM)+0.01417 (R2=0.9993),ΔI(μA)=2.224c(CC)(mM)+0.02(R2=0.996)和ΔI(μA)= 1.1885c(CC)(mM)+1.722(R2=0.952),ΔI(μA)=4.782c(CC)(mM)+0.0144 (R2=0.993)。此外,SA-Co传感器对HQ、CC和RS分子的电化学响应范围分 别为0.50μM~4950μM和4950μM~31745μM、0.50μM~1567μM和1567 μM~5909μM和0.50μM~153.5μM,三者的检出限均为0.167μM。
4、SA-Co单原子柔性传感芯片对纺织废水的检测
一种电化学柔性传感器芯片应用于纺织厂废水中二羟基苯异构体的测定。 苏州纺织厂废水排放取样,取10mL废水进行检测。取500μL废水检测,发现 有明显的RS氧化峰,而HQ氧化峰不明显。进一步研究,取2200UL检测,发 现废液中确实有少量HQ。进一步加标检测显示HQ、CC和RS有明显的氧化峰 (图6)。充分说明纺织废水中存在RS和少量HQ。然后根据(F-D)/A(%) 计算回收率,计算得到HQ、CC、RS的回收率分别为112.1%、109.2%和107.8%。
综上,本发明电化学柔性传感器芯片是一种由平均3.4个N原子在N掺 杂石墨烯基质上配位的Co(II)原子组成的单原子催化剂,用于苯二酚异构体的 检测具有优异的性能。它通过电流I-t曲线实现了0.164μM的极低LOD和 HQ、CC和RS的宽线性范围。此外,SA-Co对苯二酚的催化过程是Co*与水 中的OH-结合,再与酸性对苯二酚结合催化反应,最后催化对苯二酚生成苯醌。 这项工作为高灵敏度和大范围电化学传感器在环境污染控制应用中提供了广阔 的前景,特别是为难以区分的异构污染物的检测,同时为不同异构目标分子设计传感平台提供了科学见解。
显然,上述实施例仅仅是为清楚地说明所作的举例,并非对实施方式的限 定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它 不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所 引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.一种电化学柔性传感芯片,其特征在于,包括工作电极、参比电极和对电极,所述工作电极包含单原子钴材料,所述单原子钴材料的制备方法如下,
S1:以三聚氰胺、氨基酸和含钴化合物为前驱体,球磨混匀,得到混合物;
S2:对所述混合物进行热解,得到所述单原子钴材料。
2.如权利要求1所述的电化学柔性传感芯片,其特征在于,所述工作电极为柔性工作电极,由所述单原子钴材料为墨水,打印在导电基底上制备得到。
3.如权利要求1所述的电化学柔性传感芯片,其特征在于,所述氨基酸选自丙氨酸、半胱氨酸或络氨酸。
4.如权利要求1所述的电化学柔性传感芯片,其特征在于,所述含钴化合物为二氯化钴或醋酸钴。
5.如权利要求1、3或4所述的电化学柔性传感芯片,其特征在于,所述三聚氰胺、氨基酸和含钴化合物的质量比为40-10000:20-100:1
6.如权利要求1所述的电化学柔性传感芯片,其特征在于,所述步骤S2中,热解的温度为600-900℃,时间为1.5-4h。
7.如权利要求1-6中任一项所述的电化学柔性传感芯片在苯二酚检测中的应用。
8.如权利要求7所述的应用,其特征在于,用于判断苯二酚异构体的类型。
9.一种苯二酚检测的方法,其特征在于,将权利要求1-6中任一项所述的电化学柔性传感芯片置于含苯二酚的检测液中,检测电化学信号。
10.如权利要求9所述的苯二酚检测的方法,其特征在于,所述检测液的pH值为5-8。
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