电化学法制备CuO和ZnO一维材料及第一性原理研究

发布时间：2018-04-06 23:08

  本文选题：氧化铜　切入点：氧化锌　出处：《太原理工大学》2011年硕士论文

【摘要】：金属氧化物一维材料是高新技术领域中的一种新型功能材料,长期以来一直是材料研究的热点领域。其中CuO和ZnO一维材料更是由于具有优良的性能因而在光电催化、电池材料等领域有着广阔的应用前景。 本课题采用常温常压特点的电化学方法成功地制备出CuO和ZnO一维材料,主要研究内容为：①利用氧化铝模板(AAO)在自制离子液体中直流电沉积并经过热处理制备出CuO纳米线、纳米管,采用SEM、XRD和EDS等手段对氧化铝模板和CuO纳米线、纳米管的表面形貌以及元素组成等进行了分析表征,同时考察了氧化次数和扩孔时间对模板孔径的影响以及电沉积时间对CuO形貌的影响,并探讨了氧化铝模板形成和模板-直流电沉积法制备一维材料的原理；②采用阳极直接氧化法制备CuO和ZnO一维材料,利用SEM、XRD和EDS等手段对其表面形貌以及元素组成等进行了分析表征,利用电化学工作站测定了反应的循环伏安曲线,研究了其电化学反应过程,同时分别考察了电解液浓度、通电时间、电流密度和添加剂等因素对沉积效果的影响；③将第一性原理的方法引入一维纳米材料中来,运用基于密度泛函理论(DFT)的第一性原理从理论计算的角度来从原子层次上对CuO纳米线进行初步研究；结果表明： 1、通过SEM观察可知,利用99.5%的非高纯铝制备出的模板孔径80nm左右、孔密度大于1011个/cm2,制备出的CuO纳米管长3-4μm、管径80nm左右,CuO纳米线长3-4μm；通过XRD和EDS分析可得CuO的晶体结构；氧化铝模板的最佳制备条件为：0-5℃,40V恒压,0.3mol/L的草酸溶液中经过二次氧化共8小时并在5%的磷酸溶液中经过40min的扩孔；以AAO为模板,40-55℃,电流密度为5mA/cm2的条件下在含Cu2+的离子液体中电沉积30min可成功制备出CuO纳米管,电沉积100min可成功制备出CuO纳米线。 2、通过SEM分析可知,利用阳极直接氧化法可通过改变氧化条件分别制备出CuO纳米棒；长度大约1μm、直径90nm左右、长径比11：1左右的CuO晶须；长度大约8-10μm、直径100nm左右、长径比为1000的团簇状CuO纳米线。 3、在室温,0.3mA/cm2的电流密度下,采用阳极直接氧化法在新配置的锌酸盐溶液中可沉积松针状氧化锌晶须(直径：20-50nm,长度：200-300nm,长径比：10-15),其结构属六方晶系纤锌矿(JCPDS 36-1451)。 4、采用基于密度泛函理论的第一性原理的计算方法对块体CuO及CuO纳米线的结构性质,电子结构,差分电荷密度及布局数进行了研究。计算所得的块体CuO构型保持不变,仍为单斜,而CuO纳米线单胞构型由单斜变为三斜；CuO纳米线相对于块体相比,其Cu-O键的共价性增强；该理论计算结果为CuO一维材料的实验设计、结构、性能预测及应用提供了理论依据。
[Abstract]:Metal oxide one-dimensional material is a new functional material in the field of high and new technology. It has been a hot field of material research for a long time.Among them, CuO and ZnO one-dimensional materials have a broad application prospect in photocatalysis, battery materials and other fields because of their excellent performance.In this paper, CuO and ZnO one-dimensional materials were successfully prepared by electrochemical method at room temperature and atmospheric pressure. The main content of this study was to prepare CuO nanowires by direct current electrodeposition in self-made ionic liquids and heat treatment.The surface morphology and elemental composition of alumina template and CuO nanowires were characterized by SEM and EDS.At the same time, the influence of oxidation times and pore expansion time on the pore size of template and the influence of electrodeposition time on the morphology of CuO were investigated, and the principle of template formation and template-DC electrodeposition of one-dimensional materials were discussed.(2) One-dimensional CuO and ZnO materials were prepared by direct anodic oxidation method. The surface morphology and elemental composition of the materials were characterized by means of CuO and EDS. The cyclic voltammetry curves of the reaction were measured by electrochemical workstation.The electrochemical reaction process was studied, and the influence of electrolyte concentration, electrification time, current density and additives on the deposition effect was investigated. The first-principle method was introduced into one-dimensional nanomaterials.The first principle based on density functional theory (DFT) is used to study CuO nanowires at atomic level from the angle of theoretical calculation. The results show that:When the current density is 5mA/cm2, the CuO nanotubes can be prepared by electrodeposition of 30min in ionic liquids containing Cu2, and the CuO nanowires can be successfully prepared by electrodeposition of 100min.2. SEM analysis shows that CuO nanorods can be prepared by direct anodization by changing the oxidation conditions, the length is about 1 渭 m, the diameter of 90nm is about 1 渭 m, the aspect ratio of CuO whisker is about 11:1, the length is about 8-10 渭 m, the diameter of 100nm is about.Cluster CuO nanowires with a aspect ratio of 1000.4. The structure properties, electronic structure, differential charge density and layout number of bulk CuO and CuO nanowires are studied by using the first-principle calculation method based on density functional theory.The calculated bulk CuO configuration remains unchanged and is still monoclinic, while the CuO nanowire unit cell configuration changes from monoclinic to tridiagonal CuO nanowires, and the covalent properties of the Cu-O bond are enhanced compared with the bulk structure. The theoretical results are the experimental design of CuO one-dimensional materials.The structure, performance prediction and application provide theoretical basis.
【学位授予单位】：太原理工大学
【学位级别】：硕士
【学位授予年份】：2011
【分类号】：TB34

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