三维氮杂石墨烯功能纳米材料的制备及其电化学性能和应用研究

发布时间：2018-05-31 01:43

本文选题：三维氮杂石墨烯 + 纳米复合材料　；参考：《江苏大学》2017年硕士论文

【摘要】：三维氮杂石墨烯(3DNG)不仅具有NG良好的物理化学性能,而且具有孔隙丰富、导电性好和比表面积大等独特优势,因此被视为一种很好的支撑载体。3DNG基复合材料优异的电化学性能已在电化学领域引起关注。本论文以三维氮杂石墨烯水凝胶(3DNGH)为载体,通过水热法制备了多种复合材料,并考察了其在电催化甲醇氧化、光电化学(PEC)传感和电化学发光(ECL)生物传感等领域的应用,取得了一些有益的结果,主要内容如下:1、采用简单的一步水热法制备了Pt纳米粒子负载的3DNGH(PtNPs/3DNGH)。由多种表征手段可知,所得纳米复合物呈明显的3D多孔结构,PtNPs粒径大约为2-3 nm,且尺寸均一,分散性好。电化学性能研究表明,PtNPs/3DNGH与PtNPs/3D石墨烯和PtNPs/石墨烯相比,电化学活性面积分别为42.17 m2/g、19.18 m2/g和12.05m2/g。PtNPs/3DNGH电催化甲醇氧化的效率依次是其余二者的1.6倍和2.2倍。因此,该催化剂具有较好的催化性能,在未来高性能燃料电池中具有潜在的应用价值。2、采用简单的一步水热法制备了ZnO/3DNGH。与制备的ZnO/3D石墨烯和ZnO/NG的PEC性能对比研究发现,ZnO/3DNGH光电流强度是前者的1.5倍和2.1倍。这是由于3DNGH具有更大的比表面积,可以负载更多的Zn O纳米颗粒,同时氮的掺入提高了其导电性能,从而提高了其光电流强度。因为该材料具有比表面大、导电性好等优异性能,且可负载更多的生物识别分子。进一步以ZnO/3DNGH为载体,以辣根过氧化物酶(HRP)为模型酶,基于HRP在H_2O_2存在下,可以催化氧化4-氯-1-萘酚产生沉淀覆盖于ZnO/3DNGH的表面,导致PEC信号抑制的作用原理,构建了H_2O_2传感器。该传感器的光电流强度与H_2O_2浓度在0.001~5 mM范围内呈现良好的线性关系,检出限为3μM(S/N=3)。基于此平台,进一步构建了双酶PEC生物传感应用于b-D(+)-葡萄糖的检测,其检出限低至0.66μM(S/N=3)。该传感器具有稳定性高和重现性好等特点,可用于葡萄糖的灵敏快速地检测。3、通过简单的水热法制备了AgBr/3DNGH。研究结果表明,与AgBr负载的三维石墨烯水凝胶、3DNGH和AgBr/NG相比,AgBr/3DNGH作为鲁米诺(luminol)固定载体的ECL强度是前者的2、3和8倍。这是由于3D多孔结构可以提供较大的比表面积负载luminol分子,氮的掺入可以改善其导电性,AgBr对luminol的ECL起到催化作用等影响,从而提高了其ECL强度。进一步以制备的luminol/AgBr/3DNGH作为载体,以戊二醛为交联剂固定适配体,基于适配体与大肠杆菌(E.coli)之间能发生特异性结合进而使其ECL强度受到抑制的机理,构建了超灵敏的E.coli适配体传感器。该传感器对E.coli的响应范围在0.5~500 cfu/mL,检出限为0.17 cfu/mL(S/N=3),并成功地应用于牛奶样品的检测。
[Abstract]:3DNGs not only have good physical and chemical properties, but also have unique advantages such as rich porosity, good electrical conductivity and large specific surface area. Therefore, the excellent electrochemical properties of 3DNG matrix composites, which are regarded as a good support carrier, have attracted much attention in the field of electrochemistry. In this paper, a variety of composite materials were prepared by hydrothermal method, and their applications in the fields of electrocatalytic methanol oxidation, photochemical PECs sensing and electrochemiluminescence (ECL) biosensor were investigated. Some useful results have been obtained. The main contents are as follows: 1. The Pt nanoparticles supported 3DNGHN PtNPs / 3DNGH have been prepared by a simple one-step hydrothermal method. The results show that the PtNPs with 3D porous structure are about 2-3 nm in size, uniform in size and good in dispersion. The electrochemical performance of PtNPs / 3DNGH was compared with that of PtNPs/3D graphene and PtNPs/ graphene. The electrochemical activity area of PtNPs / 3DNGH was 42.17 m2 / g 19.18 m2 / g and the efficiency of 12.05m2/g.PtNPs/3DNGH electrocatalytic methanol oxidation was 1.6 and 2.2 times of that of the other two, respectively. Therefore, the catalyst has good catalytic performance, and has potential application value in high performance fuel cells in the future. ZnO / 3DNGH was prepared by a simple one-step hydrothermal method. Compared with the PEC properties of ZnO/3D graphene and ZnO/NG, it is found that the photocurrent intensity of ZnO / 3DNGH is 1.5 and 2.1 times higher than that of the former. This is due to the fact that 3DNGH has a larger specific surface area and can support more Zn-O nanoparticles, while nitrogen incorporation improves its electrical conductivity, thus increasing its photocurrent intensity. Because the material has large surface, good conductivity and other excellent properties, and can support more biometric molecules. Furthermore, using ZnO/3DNGH as carrier and horseradish peroxidase (HRP) as model enzyme, a H_2O_2 sensor was constructed based on the mechanism that 4-chloro-1-naphthol could be oxidized on the surface of ZnO/3DNGH by catalyzing the oxidation of 4-chlor-1-naphthol in the presence of H_2O_2, which led to the inhibition of PEC signal. The optical current intensity of the sensor has a good linear relationship with the concentration of H_2O_2 in the range of 0.001 ~ 5 mm, and the detection limit is 3 渭 m ~ (-1) S / N ~ (3 +). Based on this platform, a double enzyme PEC biosensor was further constructed for the detection of b-D (N-glucose). The detection limit of the biosensor was as low as 0.66 渭 m ~ (-1) S / N ~ (3 +). The sensor has the advantages of high stability and good reproducibility. It can be used for the sensitive and rapid detection of glucose. AgBr-3DNGH was prepared by a simple hydrothermal method. The results show that the ECL intensity of Ag-Br-3-DNGH as a luminol fixed carrier is 2 ~ 3 and 8 times higher than that of AgBr supported three-dimensional graphene hydrogel (3DNGH) and AgBr/NG. This is due to the fact that 3D porous structure can provide a large specific surface area to support the luminol molecule, and the incorporation of nitrogen can improve its electrical conductivity, such as its catalytic effect on the ECL of luminol, thus increasing its ECL strength. Furthermore, luminol/AgBr/3DNGH was used as carrier and glutaraldehyde as crosslinking agent to immobilize aptamer. Based on the mechanism of specific binding between aptamer and E. coli, the strength of ECL was inhibited. A super sensitive E.coli aptamer sensor was constructed. The response range of the sensor to E.coli is 0.5 ~ 500cfu-mL, and the detection limit is 0.17 cfu-mL ~ (-1) S / N ~ (3 +), which has been successfully applied to the detection of milk samples.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;O657.1

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