CN113960137A - {SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料及其制备方法和应用 - Google Patents
{SrP6Mo18O73}双聚单元修饰的金属有机链式传感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{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料及其制备方法和应用,属于电化学检测领域,分子式为:(H2imi)(pz)3[{Zn(H2O)2(pz)}{Zn(H2O)3(pz)}{SrP6Mo18O73}]·4H2O,pz=吡嗪,imi=咪唑;从分子学的角度出发对材料的合成进行设计,运用双刚性单环有机配体在强酸性条件下诱导合成反应,将{SrP6Mo18O73}双聚单元以十字交叠的方式引入功能性金属有机链中,组装成具有规则孔道的3D篮子型POM基金属有机‑无机聚合物,并将该传感材料应用于对DA和H2O2的双功能电化学传感检测,表现出优异的双功能电化学传感性能。
Description
技术领域
本发明属于电化学检测领域,具体涉及一种{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料及其制备方法和应用。
背景技术
过氧化氢(H2O2)是一种兼具氧化性和还原性的无机化合物,可广泛参与生化反应过程。人体新陈代谢产生的H2O2不能及时被过氧化氢酶分解,会对人体产生毒害作用。细胞内积累的H2O2会引起遗传物质损伤和基因突变,加速人体衰老和癌细胞的产生,诱发人体患神经系统疾病和器官损伤疾病。多巴胺(DA)是大脑中含量最丰富的儿茶酚胺神经递质,可用于调节中枢神经系统的各种生理功能。当多巴胺分泌的调节受损时,可能诱发帕金森病、精神分裂症、图雷特氏综合症等疾病。因此,有必要寻找一种能够快速、有效、灵敏地检测H2O2和DA含量的传感器,用于疾病预防和检测。
在现有的检测技术中,电化学方法因其优越的选择性、理想的灵敏度和较低的成本而受到了广泛的关注。然而,传统使用的专注于包括酶和蛋白质在内的生物大分子的传感器存在一系列缺点,如复杂的构建程序、弱稳定性和寿命较短等。而常见的非酶传感材料使用的金属氧化物往往因为组分相对简单,导致电压测试窗口相对较窄,在实际应用中往往只能实现单一物质的识别与检测。此外,一些拥有海胆状、球壳状等特殊结构的纳米材料,其形貌在电极制备过程很容易受到破坏,进而影响电极的稳定性。而基于多金属氧酸盐(简称:多酸,POMs)结构单元的有机-无机聚合物的非酶电化学传感器电极材料可以充分改善以上缺点,POMs团簇的引入不仅可以提高材料的稳定性,同时扩大识别检测范围,实现在特定电压下对不同物质的灵敏检测。
POMs作为众所周知的无机高核金属氧化物,由于其稳定的结构以及可逆的氧化还原活性,在材料化学中引起了极大的关注,而电化学传感检测领域是其广泛的应用之一。篮子型POMs在性质方面具有更优异的快速、可逆的多电子氧化还原能力,其在电子转移能力方面具有突出的表现,是更理想的电化学传感电极材料。但研究起步晚,发展缓慢是至今篮子化合物报道较少的重要原因。于此同时,在分子合成的角度而言篮子型POMs具有庞大位阻也是限制其发展的主要因素。在性能方面的研究也主要局限于磁学、催化和能源等方面,在电化学传感领域的研究仍是空白。
发明内容
为了解决上述技术问题,本发明提供了一种{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料及其制备方法和应用。
本发明具体是通过如下技术方案来实现的。
本发明的第一个目的是提供一种{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料,分子式为:
(H2imi)(pz)3[{Zn(H2O)2(pz)}{Zn(H2O)3(pz)}{SrP6Mo18O73}]·4H2O,
其中,pz=吡嗪,imi=咪唑。
优选的,所述传感材料是一种由链式单元构筑的含有规则孔道的3D篮子型结构。
本发明的第二个目的是提供上述{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料的制备方法,包括以下步骤:
将(NH4)6Mo7O24·2H2O、ZnAc2·2H2O、吡嗪、咪唑、SrCl2·6H2O、H3PO4和水混合搅拌,密封条件下,在160℃通过水热反应,制备{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料。
上述反应中,(NH4)6Mo7O24·2H2O、SrCl2·6H2O、H3PO4是组成POMs的成分,而组成的POMs具有可逆的多电子氧化还原能力。ZnAc2·2H2O、吡嗪、咪唑是构成金属有机单元的成分,最终与POMs组成链式和孔道结构,改善了POM基材料的比表面积,增加活性中心参与电化学反应的效率。
优选的,反应时间为102-114h。
优选的,(NH4)6Mo7O24·2H2O、ZnAc2·2H2O、吡嗪的物质的量之比为2-3:7-8:5,吡嗪、咪唑、SrCl2·6H2O的物质的量之比为5:3:5-7,(NH4)6Mo7O24·2H2O的质量与H3PO4的体积之比为(1.4-1.8)g∶2mL。
本发明的第三个目的是提供一种{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料在过氧化氢检测方面的应用。
本发明的第四个目的是提供一种{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料在多巴胺检测方面的应用。
本发明的第五个目的是提供一种玻碳复合电极,包括上述{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料。
优选的,上述玻碳复合电极的制备方法,包括以下步骤:
(1)先用氧化铝将玻碳电极进行打磨处理,之后依次在稀硝酸水溶液、乙醇和去离子水中超声清洗;
(2)将{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料研磨后,加入活性炭黑,继续研磨,之后超声分散在0.5%Nafion溶液中形成均匀的浆液;然后,将浆液滴在玻碳电极表面,在室温下干燥致形成质地均匀的薄膜。
优选的,传感材料和活性炭黑的质量之比为1:2.5-3.5,传感材料和0.5%Nafion溶液的用量比为9mg:180-200μL,玻碳电极表面滴涂浆料量7-9μL。
本发明与现有技术相比具有如下有益效果:
(1)本发明从分子学的角度出发对材料的合成进行设计,运用双刚性单环有机配体在强酸性条件下诱导合成反应,将{SrP6Mo18O73}双聚单元以新颖的十字交叠的方式引入功能性金属有机链中,组装成具有规则孔道的3D篮子型POM基金属有机-无机聚合物,并将该传感材料应用于对DA和H2O2的双功能电化学传感检测;表现出优异的DA和H2O2双功能电化学传感性能:
较高的灵敏度:对DA的灵敏度为5552.37μA·mM-1·cm-2,以及对H2O2的灵敏度为402.41μA·mM-1·cm-2;
较宽的检测范围:对DA的检测范围为0.025μM-0.356mM,以及对H2O2的检测范围3μM-8.025mM(浓度与电流之间的线性相关系数R2均为0.99);
较低的检测限:对DA的检测限为6nM,以及对H2O2的检测限为1μM(信噪比为3);此外,该电化学传感器还表现出比以往大多数传感器更优异的选择性和重现性,是作为DA和H2O2实际检测的潜在候选材料;
(2)本发明中POMs结构与金属有机链间的相互协同效应,使该传感材料既发挥POMs的可逆的多电子氧化还原能力,又能够通过金属有机单元组成的链式和孔道结构,改善材料的比表面积,增加活性中心参与电化学反应的效率,并利用微观的分子结构作用明显提升其在溶液中的宏观稳定性。
附图说明
图1为实施例1制备的材料的椭球图;
图2(a)为实施例1制备的材料的1D链式结构;(b)为实施例1制备的材料的3D多孔结构;
图3(a)为实施例1制备的材料的扫描电镜图;(b)为以实施例1制备的材料制备的玻碳复合电极表面的扫描电镜图;
图4为实施例1制备的材料在不同扫速下(20、40、60、80、100、120、140、160、180、200mV/s)的循环伏安图;
图5为实施例1制备的材料在扫描速度为50mV/s时,对不同浓度的多巴胺(a)和过氧化氢(b)的循环伏安图;
图6(a)为实施例1制备的材料对多巴胺的安培电流-时间曲线;(b)为实施例1制备的材料对过氧化氢的安培电流-时间曲线;
图7(a)为实施例1制备的材料对多巴胺的抗干扰安培电流-时间的曲线;(b)为实施例1制备的材料对过氧化氢的抗干扰安培电流-时间曲线(UA:尿酸;AA:抗坏血酸;glucose:葡萄糖;Cys:半胱氨酸;Tyr:酪氨酸;Glu:谷氨酸;Adr:肾上腺素;Ser:丝氨酸);
图8(a)为实施例1制备的材料对多巴胺感检测的重现性图;(b)为实施例1制备的材料对过氧化氢传感检测的重现性图。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案能予以实施,下面结合具体实施例和附图对本发明作进一步说明,但所举实施例不作为对本发明的限定。
下述各实施例中所述实验方法和检测方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可在市场上购买得到。
实施例1
本发明{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料的分子式为:(H2imi)(pz)3[{Zn(H2O)2(pz)}{Zn(H2O)3(pz)}{SrP6Mo18O73}]·4H2O(pz=吡嗪;imi=咪唑),其制备步骤:将(NH4)6Mo7O24·2H2O(1.608g,1.3mmol),ZnAc2·2H2O(0.812g,3.7mmol),吡嗪(0.200g,2.5mmol),咪唑(0.102g,1.5mmol),SrCl2·6H2O(0.800g,3.0mmol),H3PO4,(2mL,38mmol),以及H2O(36mL,2.0mmol)室温下混合搅拌30分钟,密封在50mL特氟龙内衬不锈钢反应釜中,160℃加热108h,自然冷却至室温后,过滤分离和收集深蓝色晶体,用蒸馏水彻底清洗,并在室温下干燥,得产物产率为51%。
实施例2
本发明{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料的分子式为:(H2imi)(pz)3[{Zn(H2O)2(pz)}{Zn(H2O)3(pz)}{SrP6Mo18O73}]·4H2O(pz=吡嗪;imi=咪唑),其制备步骤与实施例1相同,不同之处在于,(NH4)6Mo7O24·2H2O、ZnAc2·2H2O、吡嗪、咪唑、SrCl2·6H2O的物质的量之比为2:7:5:3:5;(NH4)6Mo7O24·2H2O的质量与H3PO4的体积之比为1.4g:2mL,160℃加热102h,产率为48%。
实施例3
本发明{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料的分子式为:(H2imi)(pz)3[{Zn(H2O)2(pz)}{Zn(H2O)3(pz)}{SrP6Mo18O73}]·4H2O(pz=吡嗪;imi=咪唑),其制备步骤与实施例1相同,不同之处在于,(NH4)6Mo7O24·2H2O、ZnAc2·2H2O、吡嗪、咪唑、SrCl2·6H2O的物质的量之比为3:8:5:3:7;(NH4)6Mo7O24·2H2O的质量与H3PO4的体积之比为1.8g:2mL,160℃加热114h,产率为53%。
实施例1~实施例3制备的材料性能近似,下面仅以实施例1为例,将其进行相应表征。
玻碳复合电极的制备方法:玻碳电极修饰之前先用粒径为0.3,0.1和0.05μm的氧化铝在抛光垫上进行打磨处理,之后分别在稀硝酸水溶液(1:1),乙醇以及去离子水中进行超声清理。清洁后的电极用氮气流干燥备用。称取制备好的传感材料9mg放入研钵研磨约30min后,按重量比为1:2.5-3.5(优选1:3)加入活性炭黑(AC,日本可乐丽)混合,继续研磨约30min后,超声分散在180-200μL(优选200μL)0.5%Nafion溶液中形成均匀的浆液。然后,将7-9μL(优选8μL)的浆液滴在直径为3mm玻碳电极表面,在室温下干燥致形成质地均匀的薄膜。
测试条件及内容:电化学测试使用CHI660E电化学工作站进行,以玻碳复合电极(1-AC-GCE)为工作电极,铂丝为对电极,饱和甘汞电极为参比电极共同组成三电极体系,温度为室温,氮气流下搅拌,于0.05mol/L的磷酸盐(Na2HPO4/KH2PO4)缓冲溶液(pH=7.4)中进行电化学测试。在-0.3-0.6V的电势范围,测试扫描速度为20,40,60,80,100,120,140,160,180,200mV/s下的循环伏安曲线,并在50mV/s的扫描速度下测试1-AC-GCE对H2O2和DA的电化学催化。采用安培电流-时间实验方法测定了室温下1-AC-GCE在电压-0.05V时对H2O2的电化学响应以及在电压0.35V时对DA的电化学响应。
图1椭球图展现出实施例1材料的基本结构单元及具体的原子组成和原子连接关系;图2(a)展现实施例1材料每一个基本单元在形成一维结构时的连接关系,(b)展现实施例1材料在形成的三维结构中的规则孔道。图3(a)展现实施例1材料晶体的微观形貌特征及尺寸,(b)展现实施例1材料制备的玻碳复合电极表面物质分布均匀,图4展现实施例1材料制备的电极具有良好的氧化还原活性和电化学表现。图5为实施例1中制备的材料的在扫描速度为50mV/s时,对不同浓度的多巴胺(a)和过氧化氢(b)的循环伏安图;图5展现实施例1材料制备的电极对多巴胺和过氧化氢具有良好的电催化活性。图6安培电流-时间曲线反映出电极对检测物质(多巴胺(a)和过氧化氢(b))的浓度与电流之间变化关系,结果表明电极对多巴胺和过氧化氢具有较宽的检测线和较高的灵敏度,对DA的灵敏度为5552.37μA·mM-1·cm-2,以及对H2O2的灵敏度为402.41μA·mM-1·cm-2;对DA的检测范围为0.025μM-0.356mM,以及对H2O2的检测范围3μM-8.025mM(浓度与电流之间的线性相关系数R2均为0.99),对DA的检测限为6nM,以及对H2O2的检测限为1μM(信噪比为3);图7展现出电极在检测多巴胺(a)或过氧化氢(b)时对非检测物质的具有很强的抗干扰能力。图8实施例1材料对多巴胺(a)和过氧化氢(b)在传感检测时具有良好的重现性,表明电极稳定性强,电极自身误差小。
显然,本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内也意图包含这些改动和变型在内。
Claims (10)
1.一种{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料,其特征在于,分子式为:
(H2imi)(pz)3[{Zn(H2O)2(pz)}{Zn(H2O)3(pz)}{SrP6Mo18O73}]·4H2O,
其中,pz=吡嗪,imi=咪唑。
2.根据权利要求1所述的{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料,其特征在于,所述传感材料是一种由链式单元构筑的含有规则孔道的3D篮子型结构。
3.根据权利要求1或2所述的{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料的制备方法,其特征在于,包括以下步骤:
将(NH4)6Mo7O24·2H2O、ZnAc2·2H2O、吡嗪、咪唑、SrCl2·6H2O、H3PO4和水混合搅拌,密封条件下,在160℃通过水热反应,制备{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料。
4.根据权利要求3所述的{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料的制备方法,其特征在于,反应时间为102-114h。
5.根据权利要求3所述的{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料的制备方法,其特征在于,(NH4)6Mo7O24·2H2O、ZnAc2·2H2O、吡嗪的物质的量之比为2-3:7-8:5,吡嗪、咪唑、SrCl2·6H2O的物质的量之比为5:3:5-7,(NH4)6Mo7O24·2H2O的质量与H3PO4的体积之比为(1.4-1.8)g∶2mL。
6.根据权利要求1或2所述的{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料在过氧化氢检测方面的应用。
7.根据权利要求1或2所述的{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料在多巴胺检测方面的应用。
8.一种玻碳复合电极,其特征在于,包括权利要求1或2所述的{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料。
9.根据权利要求8所述的玻碳复合电极的制备方法,其特征在于,包括以下步骤:
(1)先用氧化铝将玻碳电极进行打磨处理,之后依次在稀硝酸水溶液、乙醇和去离子水中超声清洗;
(2)将权利要求1或2所述的{SrP6Mo18O73}双聚单元修饰的金属有机链式传感材料研磨后,加入活性炭黑,继续研磨,之后超声分散在0.5%Nafion溶液中形成均匀的浆液;然后,将浆液滴在玻碳电极表面,在室温下干燥致形成质地均匀的薄膜。
10.根据权利要求9所述的玻碳复合电极的制备方法,其特征在于,传感材料和活性炭黑的质量之比为1:2.5-3.5,传感材料和0.5%Nafion溶液的用量比为9mg:180-200μL,玻碳电极表面滴涂浆料量7-9μL。
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