【作者】 尹君；

【导师】 高峰；

【作者基本信息】 安徽师范大学 ， 分析化学， 2010， 硕士

【摘要】 碳材料具有许多优点,如良好的导电性,高纯度,能够以不同的结构存在,容易制得且一般较廉价。在水溶液中,碳电极的电位窗较宽,约为-1.0～1.0V(vs.SCE);在大多数电解质溶液中碳材料具有相对化学惰性并且保持较高的电极反应性能。这些独特的性质使得碳材料作为电极材料在电化学和电分析化学研究领域具有广泛的应用。本文以碳纳米管和合成的碳微球为电极材料,对其进行功能化修饰,并基于此构建了相关电化学器件:化学/生物传感器和生物燃料电池。具体概括如下:1.碳纳米管/酚藏花红(PS-MWNTs)纳米复合物的制备及其化学/生物传感应用。以吩嗪类染料酚藏花红(phenosafranine,PS)为电催化剂,以纳米管为基质,通过吸附及π-π电子相互堆积作用,制备了碳纳米管/酚藏花红纳米复合物。基于该纳米复合物对过氧化氢电还原的催化性能,构建了过氧化氢传感,在最优化的实验条件下,该传感器的线性范围为0 - 7 mM,检测限为0.23μM。基于PS-MWNTs纳米复合物对氧气电还原的催化性能以及葡萄糖氧化酶(GOx)对底物葡萄糖的特异性生物催化功能,制备了GOx-PS-MWNTs生物纳米复合物,通过检测反应过程中被消耗的氧气量,实现了对葡萄糖的生物传感,在最优化的实验条件下,该传感器的线性范围为0 - 8 mM,检测限为0.35μM。2.合成了一种微米结构的中空碳球(CDS)。首先,研究了碳微球对NADH的催化性能,并构建了基于乳酸脱氢酶(LDH)的乳酸生物传感器;同时研究了胆红素氧化酶在碳微球修饰电极表面的直接电化学行为。基于此研制出了以LDH-CDS/GC电极作为生物阳极,以BOD-CDS/GC电极为生物阴极的无隔膜型乳酸/氧气生物燃料电池,电池的开路电位为0.45 V,最大输出功率为0.52μW/cm~2。其次,为改进催化氧化NADH的性能,在碳微球修饰电极表面电聚合亚甲基蓝(PMB),所得的PMB-CDS-GC纳米复合物对NADH具有优良的电催化性能。基于此研制出乳酸生物传感器,并且构建了以LDH-PMB-CDS/GC为生物阳极,以BOD-CDS/GC为生物阴极的无隔膜型乳酸/氧气生物燃料电池。该电池的开路电位为0.6 V最大输出功率为3.13μW/cm~2。更多还原

【Abstract】 Carbon Materials possess many distinguished characteristics including good electrical conductivity, high purity, diversified structures, cheap, and more readily available. Carbon materials have a wide potential window (-1.0～1.0V vs.SCE) in aqueous solution. In addition, carbon materials are relatively chemically inert and can keep fairly high surface activity. These distinct characteristics essentially endow carbon materials with extensive applications in electrochemistry and electroanalytical chemistry.In this paper, two kinds of carbon materials, carbon nanotube and carbon hollow sphere, are used as electrode materials and functionalized rationally. Based on this, relative electrochemical devices such as chemo/biosensing and biofuel cell are constructed. The details are summarized as follows:1. Preparation of carbon nanotube/phenosafranine nanocomposites (PS-MWNTs) and its chemo/biosensing applications. The PS-MWNTs nanocomposites, in which phenosafranine (PS) used as electrocatalyst and MWNTs as electrode substrate, are prepared via adsorption andπ-πelectronic stack. A hydrogen peroxide (H2O2) sensor is constructed based on electrocatalytic activity of PS-MWNTs nanocomposite to H2O2. Under the optimum experimental conditions, the linear range of the sensor is 0-7 mM with a detection limit of 0.23μM. The GOx-PS-MWNTs bionanocomposites, in which GOx (glucose oxidase) is used as biocatalyst to glucose oxidation and PS-MWNTs as electrocatalyst to oxygen reduction, are also prepared, and as thus a glucose sensor is constructed based on the amount of oxygen comsumed in the glucose oxidation reaction catalysed by GOx. Under optimum experimental conditions, the linear range for glucose sensing is 0-8 mM, with a detection limit of 0.35μM.2. A micro-structured carbon hollow spheres (CPS) are synthesized. Firstly, the catalytic activity of CPS to NADH oxidation is studied and also a lactate biosensor based on lactate dehydrogenase (LDH) is constructed. The direct electrochemistry of bilirubin oxidase (BOD) on CDS/GC electrode is investigated. And as thus a membrane-less enzymatic lactate/O2 biofuel cell is constructed using LDH-CDS/GC electrode as bioanode and BOD-CDS/GC as biocathode. The biofuel cell is found to have open potential of 0.45 V and a maximum power output of 0.52μW/cm~2. Secondly, in order to improve the catalytic activity to NADH oxidation, a electrocatalyst to NADH oxidation, poly(methyl Blue) is further immobilized on CDS/GC electrode via electropolymerization. And as thus another lactate biosensor based on lactate dehydrogenase is constructed and also a membrane-less enzymatic lactate/O2 biofuel cell using LDH-polyMB-CDS/GC as bioande and BOD-CDS/GC as biocathode is also construted. The biofuel cell is found to have open potential of 0.6 V and a maximum power output of 3.13μW/cm~2.更多还原