石墨烯功能化聚酰亚胺柔性修饰电极的制备及其在传感器和光电转换方面的应用

发布时间：2018-05-09 13:58

本文选题：还原氧化石墨烯 + 聚酰亚胺　；参考：《兰州大学》2017年博士论文

【摘要】：聚酰亚胺基薄膜修饰电极由于其良好的化学稳定性和可加工性在光电器件的研发中受到越来越多的关注。本博士论文制备了具有导电性的还原氧化石墨烯/聚酰亚胺(rGO/PI)柔性复合薄膜,并以此柔性薄膜电极为基底,在其表面修饰不同类型的纳米半导体材料;使用扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)等物理化学测试技术以及循环伏安法(CV)、线性扫描伏安法(LSV)、脉冲伏安法(DPV)以及开路电位-时间法(OCP-t)等电化学方法对复合薄膜修饰电极的形貌、结构与性能进行了系统表征;研究了修饰薄膜电极在传感器和光电转换中的应用。主要内容包括:1. Mo修饰的rGO/PI薄膜电极的制备及多巴胺的灵敏性检测通过一步合成法制备了 Mo掺杂的rGO/PI多巴胺(DA)传感器,结合XRD和XPS技术证明Mo以MoO2的形式存在于rGO/PI薄膜中。在最优条件下,由LSV法测得Mo-rGO/PI电极上的电化学信号强度与 DA浓度有可信的正相关关系,其线性范围为0.1- 2000 uM,检测限为0.021 uM(S/N=3);对尿酸和抗坏血酸具有很强的抗干扰性,稳定性和重复性良好;用该传感器测定了人血清和医用针剂实际样品中DA的含量,所得测定结果、回收率和相对标准偏差等数据令人满意。2.乙酰胆碱酯酶修饰的Au-MoS2-rGO/PI柔性薄膜传感器的构建及其对对氧磷的测定采用光还原法在MoS2-rGO/PI柔性薄膜电极表面制备了金纳米颗粒(AuNPs),TEM表征结果显示AuNPs的平均直径约为10nm。DPV结果显示乙酰胆碱酯酶修饰的AuNPs-MoS2-rGO/PI柔性薄膜电极催化水解氯化乙酰胆碱产生明显的电化学信号;该电化学信号强度与对氧磷浓度间存在较宽的线性范围(0.005-0.15 ug/mL),较低的检测限(0.0014 ug/mL)和较高的灵敏度(4.44 uA/ug mL-1);所表现的重复性和稳定性良好。该柔性薄膜传感器能够用于实际样品中对氧磷的测定。3. MoSe_2在柔性薄膜rGO/PI表面的生长及其电催化和光电催化析氢性能的研究通过电化学沉积法在rGO/ PI柔性基底电极表面制备了 MoSe_2。通过SEM、TEM、XRD、XPS、电化学等技术对MoSe_2的形貌、结构与性能进行了表征。实验结果证明MoSe_2-rGO/PI复合薄膜电极具有优良的的光电转换效应,其光开关实验产生的电位差值能够达到0.45 V,光电流响应时间在0.6 s以内;此外MoSe_2-rGO/PI复合薄膜电极对氢离子还原有显著的催化作用,在-0.3 V时的析氢电流达到7.9 mAcm-2;在光照的条件下,光能有效地促进MoSe_2-rGO/PI复合薄膜电极催化析氢。4.基于rGO/PI基底表面稀磁半导体ZnMnSe_2的制备及其光电性质的研究采用电化学沉积法在rGO/PI薄膜电极表面制备了稀磁半导体ZnMnSe_2。通过SEM、XRD、TEM等分析方法对rGO/PI表面的ZnMnSe_2进行了形貌与结构的研究,发现rGO/PI表面的ZnMnSe_2具有独特的纳米片网孔结构。通过OCP-t实验得出ZnMnSe_2-rGO/PI电极具有良好的光电性质,其电位差值能够达到270 mV,相对于二元化合物ZnSe和MnSe而言其光电性能明显提高。该复合薄膜具有良好的磁性,是典型的铁磁性半导体材料。5. ZnSe在新型基底CNTs/PVA电极表面的原位生长及其光电性质的研究用i-t交替沉积的方法在新的柔性薄膜电极碳纳米管/聚乙烯醇(CNTs/PVA)表面制备了 ZnSe,从而得到ZnSe-CNTs/PVA复合薄膜电极。实验中通过改变Zn与Se的浓度,研究了原子比例Zn: Se对化合物(ZnxSe1-x)形貌的影响,发现ZnSe的形貌是最均匀单一的,由纳米棒组成。通过OCP-t实验研究了相似类型三种化合物的光电性质,发现均为p型半导体,且均具有良好的光电性质,其中ZnSe的光电效应是最好的。
[Abstract]:Polyimide based film modified electrodes have attracted more and more attention in the development of optoelectronic devices because of their good chemical stability and machinability. This paper has prepared a conductive reduced graphene oxide / polyimide (rGO/PI) flexible composite film, which is based on the flexible thin film electrode and modified on its surface. The nano semiconductor materials of the same type are modified by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X ray photoelectron spectroscopy (XPS), X ray diffraction (XRD), cyclic voltammetry (CV), linear sweep voltammetry (LSV), pulse voltammetry (DPV) and open circuit potential time (OCP-t), and other electrochemical methods The application of modified thin film electrode in sensor and photoelectric conversion is studied. The main contents include: the preparation of 1. Mo modified rGO/PI film electrode and the sensitivity detection of dopamine, the Mo doped rGO/PI dopamine (DA) sensor is prepared by one step synthesis method, combined with XRD and XPS technology. It is proved that Mo exists in the form of rGO/PI in the form of MoO2. Under the optimal conditions, there is a credible and positive correlation between the electrochemical signal intensity on the Mo-rGO/PI electrode and the concentration of DA by LSV method. The linear range is 0.1- 2000 uM and the detection limit is 0.021 uM (S/N=3); it has strong anti-interference, stability and repeatability to uric acid and antiblood acid. Well, the content of DA in real samples of human serum and medical needle was measured with this sensor. The results of the determination, recovery and relative standard deviation were satisfactory for the construction of the Au-MoS2-rGO/PI flexible thin film sensor modified by.2. acetylcholinesterase and the determination of phosphor by photoreduction in MoS2-rGO/PI flexible thin film Gold nanoparticles (AuNPs) were prepared on the surface of the electrode. The TEM characterization showed that the average diameter of AuNPs was about 10nm.DPV. The AuNPs-MoS2-rGO/PI flexible membrane electrode modified by acetylcholinesterase catalyzed the hydrolysis of acetylcholine to produce obvious electrochemical signals, and the intensity of the electrochemical signal was wide with the concentration of oxyphosphoric acid. The range (0.005-0.15 ug/mL), lower detection limit (0.0014 ug/mL) and higher sensitivity (4.44 uA/ug mL-1); the reproducibility and stability are good. The flexible thin film sensor can be used to determine the growth of.3. MoSe_2 on the surface of the flexible film rGO/PI and the electrocatalysis and Photoelectrochemical Performance of hydrogen evolution in the actual samples. The morphology, structure and properties of MoSe_2. were characterized by electrochemical deposition on the surface of rGO/ PI flexible substrate by SEM, TEM, XRD, XPS, electrochemistry and other techniques. The experimental results show that the MoSe_2-rGO/PI composite film electrode has excellent photoelectric conversion effect and the potential difference energy produced by the optical switch experiment can be produced. The response time of the photocurrent is within 0.6 s enough to reach 0.45 V, and the MoSe_2-rGO/PI composite film electrode has a significant catalytic effect on the hydrogen ion reduction, and the hydrogen evolution current at -0.3 V reaches 7.9 mAcm-2. Under the light conditions, the light energy can effectively promote the catalytic hydrogen evolution of the MoSe_2-rGO/PI composite film electrode based on the dilute magnetic half surface of the rGO/PI substrate surface. Study on the preparation and photoelectrical properties of conductor ZnMnSe_2, the morphology and structure of the rGO/PI surface ZnMnSe_2 were studied by electrochemical deposition on the surface of rGO/PI thin film electrode by the methods of SEM, XRD, TEM and other analytical methods. It was found that ZnMnSe_2 of the rGO/PI surface has a unique nanoscale mesh structure. Through O, ZnMnSe_2 has been found. The CP-t experiment shows that the ZnMnSe_2-rGO/PI electrode has good photoelectric properties and its potential difference can reach 270 mV. Compared with the two element compound ZnSe and MnSe, the photoelectric property is obviously improved. The composite film has good magnetic properties. It is a typical ferromagnetic semiconductor material.5. ZnSe in situ growth on the surface of the new base CNTs/PVA electrode. The study of the optoelectronic properties of ZnSe was prepared on the surface of a new flexible film electrode carbon nanotube / polyvinyl alcohol (CNTs/PVA) on the surface of a new flexible thin film electrode by I-T, and the ZnSe-CNTs/PVA composite film electrode was obtained. In the experiment, the influence of the atomic proportion Zn: Se on the morphology of the compound (ZnxSe1-x) was studied by changing the concentration of Zn and Se, and ZnSe was found. The morphology is the most uniform and single, composed of nanorods. The photoelectric properties of three similar types of compounds were investigated by OCP-t experiments. All of them were found to be p type semiconductors with good photoelectric properties, and the optoelectronic effect of ZnSe was the best.

【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O646.54;TB383.2

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