【作者】 陈洁；

【导师】 叶建山；

【作者基本信息】 华南理工大学 ， 分析化学， 2016， 硕士

【摘要】 化学修饰电极(CME)的问世,突破了传统意义上的电化学裸电极/电解液界面的范畴,开创了人为控制电极界面微结构的新领域。化学修饰电极强调了修饰剂对电极/电解液界面的修饰,修饰电极可利用丰富的有机物、无机物、配合物、聚合物和生物物质等的多种功能基团,还可利用多孔、微米和纳米等材料的特殊形貌,在电极表面进行各式各样的设计,实现电极表面预定的功能,提高选择性和灵敏度。本论文以铜纳米材料的制备为基础,研究了其在过氧化氢(H2O2)及酚类电化学传感器中的应用,本论文主要研究内容如下:(1)本实验研究过程中,通过水热反应法及静置挥发法成功获得三氮烯铜的配合物;另外通过氧化还原法我们也获得了铜碳纳米材料。为了探究材料的表面形态及结构特征,我们采用SEM,EDS,XRD,XPS,UV-Vis等表征手段进行分析和验证。(2)利用三氮烯铜配合物中所含的S原子与Au通过共价键,将三氮烯铜组装到金电极(Au)表面,并考察了修饰电极对H2O2的电化学行为。由于三氮烯铜本身含有的催化性能,成功将其组装到Au电极表面后,形成的新的修饰电极对过氧化氢是非电催化机理。研究表明,H2O2的线性范围为0.05-60μM,检出限(S/N=3)为0.042μM。此外,本方法可用于医用消毒液中H2O2含量的测定。(3)通过简单、快速的方法合成铜纳米材料,并成功将其组装到玻碳(GC)电极表面,并实现了对对苯二酚(HQ)及邻苯二酚(CC)的同时测定。研究表明,铜纳米材料电催化性能不同于多壁碳纳米管材料,在实验条件优化后,HQ的线性范围是3μM–120μM,检出限(S/N=3)为1.2μM;CC的线性范围是4μM–115μM,检出限是(S/N=3)为1.5μM。而且我们构建的新型电化学传感器有望在HQ与CC的实际测定得到广泛应用。更多还原

【Abstract】 The advent of the theory of chemical modified electrode(CME) had broken through the traditional concept of electrode/electrolyte interface and initiated a new research field of controllable electrode interface.The CME can be endowed by assembling or clipping the variety of functional groups of organic,inorganic compounds complexes and polymers still the special morphology of porous, micro and nanometer materials. By using the unique modifier, the selectivity and sensitivity can be improved and the intended function can be realized. In this thesis, the methods were studied to synthesis copper nanaomaterials and prepare the modified electrodes for the detection of hydrogen peroxide(H2O2) and hydroquinone(HQ), catechol(CC). The main points of this thesis are briefly summarized as follow:1. During this experiments, ligend and copper complex were synthesised through hydrothermal and standing volatilization; besides the copper nanomaterials were synthesised through oxidation and reduction copper(II) ion. Scanning electron microscopy(SEM), X-ray photoelectron spectroscopy(XPS), X-ray diffraction(XRD) and UV-Vis were used to explore the morphology and chemical structure of copper complex and copper nanomaterials.2. The copper complex was immobilized on the surface of Au electrode through Au-S covalent bonds to form a self-assembled monolayer. Under the optimum conditions, the ultralow detection limit of 0.042 μM(S/N= 3) is achieved and the linear concentration is 0.05-60 μM with the correlation coefficients of 0.9988. The modified electrode allowed sensitive,stable and fast electrochemical sensing of H2O2. The analysis of medical disinfection solution real samples was performed using the proposed method and the satisfactory results.3. A green, fast and facile approach for the preparation of nanomaterial to make the modified glass carbon electrode(GCE) is achieved. Then the modified GCE was applied for the simultaneous determination of HQ and CC. Under the optimized condition, the calibration curves for HQ and CC were obtained in the range of 3 to 120 μM for HQ and 4 to 115 μM for CC, with detection limits(S/N = 3) of 1.2 μM and 1.5 μM, respectively. Therefore, our research can provide a promising sensing platform for a variety of electroanalysis applications.更多还原