剥离层状纳米片与金属卟啉自组装行为及电催化性能研究

发布时间：2018-10-22 09:41

【摘要】：无机层状化合物材料因其具有独特的结构特性,能够通过插层技术将功能性的客体分子引入到主体层间而不破坏基本的层状结构,并且获得的复合材料具有高度的稳定性。通过插层反应得到的纳米复合材料,兼具层状主体和客体分子的优异性能,在电化学及生物传感器、光学、催化材料、吸附分离和纳米器件等领域表现出潜在的应用价值。本文选择阳离子型层状化合物(α-Zr P、KLa Nb2O7)和阴离子型层状化合物(Cu2(OH)3NO3、Zn5(OH)8(NO3)2·2H2O、Co-Al LDHs)为层状主体,铵盐型金属卟啉(Mn TMPy P、Fe TMPy P、Co TMPy P)和磺酸盐型金属卟啉(Mn TSPP)为客体分子,制备了8种新型的无机-有机复合材料,并考察了其电化学性质。主要研究内容如下:1.分别用稍加修改的氟配法和高温固相法制备了主体材料α-Zr P和KLa Nb2O7,采用剥离法(α-Zr P主体材料和酸化产物HLa Nb2O7分散到一定体积的TBAOH水溶液中)将其剥离成纳米片层,对其进行zeta电位及TEM测定,然后与铵盐型金属卟啉(Mn TMPy P、Fe TMPy P、Co TMPy P)进行自组装,获得5种层状复合材料,并通过XRD、IR、UV-vis、SEM、TG-DTA等表征手段对其进行分析。2.分别采用恒压滴液漏斗滴加法和尿素水解法制备主体材料Cu2(OH)3NO3、Zn5(OH)8(NO3)2·2H2O和Co-Al-CO3 LDHs,在氮气氛围中进行剥离(将Cu2(OH)3NO3、Zn5(OH)8(NO3)2·2H2O和离子交换产物Co-Al-NO3 LDHs分散到一定体积的甲酰胺溶剂中),对得到的纳米片分散液进行zeta电位及AFM测定,然后加入氮气饱和的磺酸盐型金属卟啉溶液(Mn TSPP),获得3种层状复合材料,并利用XRD、IR、UV-vis、SEM表征手段对其进行测定。3.采用三电极体系,应用循环伏安法(CV)和微分脉冲法(DPV)测试了修饰电极Mn TMPy P-α-Zr P/GCE、Co TMPy P-α-Zr P/GCE以及Mn TMPy P-La Nb2O7/GCE、Fe TMPy P-La Nb2O7/GCE、Co TMPy P-La Nb2O7/GCE在中性磷酸盐缓冲溶液中的电化学性能,结果表明修饰电极对氧气、亚硝酸钠、抗坏血酸和一水合肼有一定的催化作用。4.利用上述相同的电化学测试方法,考察了修饰电极Mn TSPP-Cu2(OH)3NO3/GCE、Mn TSPP-Zn5(OH)8(NO3)2·2H2O/GCE和Mn TSPP/Co-Al LDHs在中性磷酸盐缓冲溶液中的电化学性质,结果表明Mn TSPP-Zn5(OH)8(NO3)2·2H2O/GCE和Mn TSPP/Co-Al LDHs复合薄膜中的功能性金属卟啉分子MnTSPP表现出较好的电子转移特征。
[Abstract]:Because of its unique structural properties, inorganic layered compound materials can introduce functional guest molecules into the host layer by intercalation without destroying the basic layered structure, and the obtained composites have a high degree of stability. The nanocomposites prepared by intercalation reaction have both excellent properties of layered host and guest molecules, and have shown potential applications in electrochemical and biosensor, optics, catalytic materials, adsorption separation and nanodevices. In this paper, cationic and anionic layered compounds (Cu2 (OH) _ 3NO _ 3N _ 3Zn _ 5 (OH) _ 8 (NO3) _ 2H _ 2O _ (Co-Al) LDHs) are selected as the layered host, and the ammonium salt metalloporphyrin (Mn TMPy PnFe TMPy PCoCo TMPy P) and sulfonate metalloporphyrin (Mn TSPP) are used as guest molecules. Eight new inorganic-organic composites were prepared and their electrochemical properties were investigated. The main contents are as follows: 1. The main materials 伪-Zr P and KLa Nb2O7, were prepared by slightly modified fluorine matching method and high temperature solid state method respectively. The 伪-Zr P main material and the acidified product HLa Nb2O7 dispersed in a certain volume of TBAOH aqueous solution were peeled off into nano-lamellae by stripping method. The zeta potential and TEM were measured, and then self-assembled with ammonium metalloporphyrin (Mn TMPy), Fe, TMPy and Co TMPy P). Five kinds of laminated composites were obtained and analyzed by means of XRD,IR,UV-vis,SEM,TG-DTA and other characterization methods. 2. The main materials Cu2 (OH) _ 3NO _ 3n _ 3n _ 5 Zn _ 5 (OH) _ 8 (NO3) _ 2 2H2O and Co-Al-CO3 LDHs, were prepared by constant pressure drop trickle drop addition method and urea hydrolysis method respectively in nitrogen atmosphere. (Cu2 (OH) _ 3no _ 3n _ 3n _ 3n _ 5 Zn _ 5 (OH) _ 8 (NO3) _ 22H2O and the ion exchange product Co-Al-NO3 LDHs were dispersed in a certain volume of formamide solvent). The zeta potential and AFM of the nanoparticles were measured. Then three kinds of laminated composites were obtained by adding nitrogen-saturated sulfonate metalloporphyrin (Mn TSPP),) solution and determined by XRD,IR,UV-vis,SEM characterization. The electrochemical properties of modified Mn TMPy P- 伪-Zr P- / GCE-Co TMPy P- 伪-Zr P/GCE and Mn TMPy P-La Nb2O7/GCE,Fe TMPy P-La Nb2O7/GCE,Co TMPy P-La Nb2O7/GCE in neutral phosphate buffer solution were measured by cyclic voltammetry (CV) and differential pulse method (DPV) with three-electrode system. The results showed that the modified electrode could catalyze oxygen, sodium nitrite, ascorbic acid and hydrazine hydrate. The electrochemical properties of mn TSPP-Zn5 (OH) 8 (NO3) 2 2H2O/GCE and Mn TSPP/Co-Al LDHs at the modified Mn TSPP-Cu2 (OH) 3NO 3 / GCEC TSPP-Zn5 (OH) 8 (NO3) 2 2H2O/GCE in neutral phosphate buffer solution were investigated by using the same electrochemical method mentioned above. The results show that the functional metalloporphyrin molecule MnTSPP in Mn TSPP-Zn5 (OH) _ 8 (NO3) _ 2 2H2O/GCE and Mn TSPP/Co-Al LDHs composite films exhibits good electron transfer characteristics.
【学位授予单位】：中国矿业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TB33

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