【作者】 高娟；

【导师】 吴灿；

【作者基本信息】 湖北大学 ， 化学， 2021， 硕士

【摘要】 如今,地球的生态系统不断受到各种环境污染物的侵害。与此同时,环境污染物的生物积累性和长期持久性也被认为是无声杀手,严重影响着人类的健康和社会经济发展。因此,开发快速、有效的环境监测手段是全球都在解决的科学问题。电化学传感器具有分析速度快、灵敏度高、选择性好、所需试样量少、操作简单、适于在线分析、应用范围广等优点,在环境污染物的快速、灵敏检测方面具有极大的应用潜力。本文分别以沸石咪唑类MOFs的功能化材料及衍生材料为电极界面基本构筑单元,以环境污染物雌酚酮和萘酚异构体为目标分析对象,构建了两种高灵敏的环境污染物电化学传感平台。具体工作内容如下:1.以多面体形貌的ZIF-8（Zn-MOF）为前驱体,HAu Cl₄为金属源,首先通过离子交换策略获得了双金属AuZn-MOF;随后以Na BH₄为还原试剂,采用原位化学还原的方法制备得到了超细Au纳米颗粒功能化的双金属AuZn-MOF复合物（USAuNPs/AuZn-MOF）。受益于超细Au纳米颗粒优异的电化学活性,USAuNPs/AuZn-MOF复合物对环境污染物雌酚酮的氧化显示了高的电化学活性。基于此,构建了一种用于雌酚酮快速检测的高灵敏电化学传感平台,线性范围为0.05μM-5μM,检出限为12.3 n M,灵敏度为101.25μAμM^-1 cm^-2,将其用于实际样品的检测,显示了满意的结果。2.以多面体形貌的ZIF-67（Co-MOF）为前驱体,首先在惰性氛围下经高温热解,获得氮掺杂的多孔碳框架（N-C）,随后以植酸为磷源,将吸附植酸的N-C在高温下进行活化,获得了氮磷共掺杂的多孔碳框架（N,P-C）。相比于单掺杂的多孔碳框架,氮磷共掺杂的多孔碳框架表面缺陷增多、电化学活性面积增大。受益于N,P-C显著增强的电化学性能,其对环境污染物1-萘酚和2-萘酚的电化学氧化表现出了更优异的活性。基于此,构建了一种用于同时高灵敏检测1-萘酚和2-萘酚的电化学传感平台,1-萘酚和2-萘酚的检测线性范围均为25 n M-2μM,检出限分别为8.0 n M和7.2 n M,灵敏度分别为87.3μAμM^-1 cm^-2和84.6μAμM^-1 cm^-2。更多还原

【Abstract】 Today,the earth’s ecosystem is constantly being attacked by various environmental pollutants.At the same time,the biological accumulation and long-term persistence of environmental pollutants are also considered as silent killers,which seriously affect human health and social and economic development.Therefore,the development of rapid and effective means of environmental monitoring is a scientific problem that the world is being to solve.Electrochemical sensors have the advantages of fast analysis speed,high sensitivity,good selectivity,less sample required,simple operation,suitable for online analysis,wide application range,and so on.They have great application potential in the rapid and sensitive detection of environmental pollutants.In this study,two highly sensitive electrochemical sensing platforms for environmental pollutants were constructed by using the functionalized and derived materials of zeolitic imidazolate frameworks as the basic building units of the electrode interface,and using estrone and naphthol isomers as the target analysis objects,respectively.Specific work contents are as follows:1.The bimetallic AuZn-MOF was obtained by ion exchange strategy using polyhedral ZIF-8（Zn-MOF）as precursor and HAu Cl₄ as metal source.Subsequently,using Na BH₄ as reduction reagent,bimetallic AuZn-MOF composite functionalized with ultrasmall Au nanoparticles（USAuNPs/AuZn-MOF）was prepared by in situ chemical reduction.Benefit from the excellent electrochemical activity of ultrasmall Au nanoparticles,the USAuNPs/AuZn-MOF composite showed high electrochemical activity for the oxidation of estrone,which is an environmental pollutant.Based on this,A highly sensitive electrochemical sensing platform for rapid detection of estrone was constructed.The linear range of estrone was 0.05μM-5μM,the detection limit was 12.3 n M,and the sensitivity was 101.25μAμM^-1 cm^-2.It was used for the detection of real samples,and the results were satisfactory.2.The polyhedron ZIF-67（Co-MOF）was used as the precursor to obtain the nitrogen-doped porous carbon framework（N-C）by high temperature pyrolysis in an inert atmosphere.Then,the N-C adsorbed by phytic acid was activated at high temperature to obtain the N-P co-doped porous carbon framework（N,P-C）.Compared with the single-doped porous carbon frameworks,the surface defects of the N、P co-doped porous carbon framework increased and the electrochemical activity area increased.Benefit from the N,P-C framework showed more excellent activity for the electrochemical oxidation of environmental pollutants 1-naphthol and2-naphthol.Based on this,a sensing platform for simultaneous high-sensitivity electrochemical detection of 1-naphthol and 2-naphthol was constructed.The linear range of 1-naphthol and 2-naphthol was 25 n M-2μM,the detection limits were 8.0 n M and 7.2 n M,respectively.The sensitivity of 1-naphthol and 2-naphthol was 87.3μAμM^-1 cm^-2 and 84.6μAμM^-1 cm^-2.更多还原