【作者】 兰杰；

【导师】 宋杰；

【作者基本信息】 上海交通大学 ， 仪器仪表工程（专业学位）， 2020， 硕士

【摘要】 糖尿病是一种以体内血糖水平异常为典型特征的慢性疾病,近年来成为严重危害公众健康的疾病之一,对葡萄糖含量进行可靠检测对数以百万计的糖尿病患者日常血糖水平的监测具有重大意义。在众多检测手段中,以葡萄糖氧化酶为核心的酶葡萄糖传感器以高灵敏度和良好选择性为特征,是当今葡萄糖生物传感器市场的主流产品。然而,由于酶对环境条件要求苛刻以及固定技术复杂成本高,酶葡萄糖传感器的进一步发展受到阻碍,无酶葡萄糖传感器受到研究者的青睐。作为无酶葡萄糖传感器的活性材料,贵金属材料具有出色的催化活性,但极低的自然储量和高昂的生产成本限制了其大规模的应用。而高丰度和低成本的铜、镍、钴等过渡金属材料在大量的研究工作中显示出了优异的电催化氧化能力,展现出了替代贵金属材料成为无酶葡萄糖传感器电极材料的巨大潜力。近年来,钴基氢氧化物凭借内在的催化活性和良好的稳定性在大量的实例中显示出了优异的电催化氧化能力。本论文的主要工作是钴基氢氧化物作为无酶葡萄糖传感器电极材料的性能研究。本文采用一步溶剂热法在泡沫镍基底上生长钴基氢氧化物,构建Co HS/Ni Foam和其掺杂体Co Ni HS/Ni Foam、Co Fe HS/Ni Foam工作电极,考察其对葡萄糖电催化氧化的能力和作为无酶葡萄糖传感器电极材料的实际意义。本论文主要研究内容如下:1.以泡沫镍作为自支撑导电基底,采用溶剂热法制备出颗粒状和片层状氢氧化钴,构建氢氧化钴/泡沫镍工作电极。在水介质中,二维片层状氢氧化钴相比于颗粒状氢氧化钴具有更好的电催化氧化能力。2.以氢氧化钴纳米片和泡沫镍的复合结构作为葡萄糖无酶传感器的电极材料,在含有葡萄糖的碱性溶液中考察其对葡萄糖的电催化氧化能力。结果表明,该传感器灵敏度为3904μA·m M^-1·cm^-2,线性范围为0.2～3.6m M,检出限为0.017 m M（S/N=3）,响应时间小于1s,并且具有良好的抗干扰性和稳定性。3.以泡沫镍作为自支撑导电基底,采用溶剂热法制备出氢氧化钴纳米片,并在合成过程中掺入不同比例的镍元素和铁元素,构建钴-镍双氢氧化物和钴-铁双氢氧化物葡萄糖无酶传感器。实验结果表明,掺杂镍、铁过渡金属元素可以有效改善氢氧化钴的电催化氧化能力,其中掺杂10%的镍元素或50%的铁元素具有最佳的改善效果。更多还原

【Abstract】 Diabetes is a chronic disease characterized by abnormal blood glucose level in the body.In recent years,it has become one of diseases that seriously endanger public health.It is of great significance to monitor the daily blood glucose level of millions of diabetic patients.In many detection methods,glucose biosensor with glucose oxidase as the core is characterized by high sensitivity and good selectivity,which is the mainstream product of glucose biosensor market.However,the further development of enzyme glucose sensor is hindered due to the strict requirements of enzyme on environmental conditions and the high cost of fixed technology,and non-enzyme glucose sensor is favored by researchers.As an active material for enzyme-free glucose sensors,precious metal materials have excellent catalytic activity,but their large-scale application is limited by their low natural reserves and high costs.The transition metals such as copper,nickel and cobalt with high abundance and low cost have shown excellent electrocatalytic oxidation ability,showing a great potential to replace precious metals as electrode materials for enzyme-free glucose sensor.In recent years,cobalt hydroxides have shown excellent electrocatalytic oxidation ability due to their inherent catalytic activity and good stability.The main work of this paper is to study the properties of cobalt hydroxides as electrode material of enzyme-free glucose sensor.We used solvothermal method to grow cobalt hydroxides on the foamed nickel,constructed Co HS/Ni Foam and its doped Co Ni HS/Ni Foam and Co Fe HS/Ni Foam,and investigated their ability to catalyze glucose oxidation and their practical significance as electrode materials for enzyme-free glucose sensors.The main contents of this paper are as follows:1.using foamed nickel as self-supporting conductive substrates,granular and lamellar cobalt hydroxides were prepared by solvothermal method,and cobalt hydroxide/nickel foam working electrode was constructed.Two-dimensional lamellar cobalt hydroxide has better electrocatalytic oxidation ability than granular cobalt hydroxide in water medium.2.the composite structure of cobalt hydroxide nanosheets and nickel foam was used as electrode material for glucose enzyme-free sensor,and its ability to catalyze glucose oxidation was investigated in alkaline solution containing glucose.The results show that the sensitivity of the sensor is 3904μA·m M^-1·cm^-2,the linear range is 0.2～3.6 m M,the detection limit is 0.017m M（S/N=3）,the response time is less than 1s,and it has good anti-interference and stability.3.using foamed nickel as self-supporting conductive substrates,cobalt hydroxide nanosheets were prepared by solvothermal method,and different proportion of nickel or iron elements were added in the synthesis process,and cobalt-nickel double hydroxide and cobalt-iron double hydroxides glucose enzyme-free sensor were constructed.The experimental results show that doping nickel or iron transition metal elements can improve the electrocatalytic oxidation ability of cobalt hydroxides,in which doping 10%nickel or 50%iron element has the best effect.更多还原