摘 要

人类社会经过多次的工业革命，特别是第二次工业革命以来，社会生产力得到前所未有的提高，同时工业农业的发展也带来了巨大的污染问题，在这些问题中，废水中有机污染物的降解问题十分突出，这些有机污染物不能自然降解，对环境尤其是水环境危害极大。目前国际国内许多实验室都在寻求更好的降解手段，通过掺杂Cu₂O催化降解污染物便是其中一个很热门的领域。

氧化亚铜（Cu₂O）英文名称Copper（I）Oxide，其作为一种典型的P型半导体，具有良好的光催化性能，纳米级别的氧化亚铜（Cu₂O）由于其独特的物理化学性质，在环境污染处理、能源转化方向具有十分重要的作用。

由于单相半导体较高的量子复合效率可能不利于光催化反应的进行,本文以金属Cu和Cu₂O作为添加剂对Cu₂O进行修饰,运用简单环保的液相还原法，绿色合成Cu₂O/Cu和Cu₂O/CuO纳米晶粒，通过生物矿化过程，引入生物大分子，在相对温和的条件下反应生成所需复合材料，研究Cu₂O/Cu复合材料的制备、光催化降解等问题，并对其催化机制进行简单的探讨，寻找催化性能较好的复合体系。

本文采用CuCl₂·2H₂O为前驱体溶液，通过控制改变还原剂L-抗坏血酸（L-ascorbic acid）的加入量以及NaOH溶液的浓度，合成不同形貌，不同粒径的纳米晶粒，并且利用X射线衍射（XRD）分析其成分，利用扫描电子显微镜（SEM）分析晶粒大小以及形貌，利用光催化性能测试对其催化性能进行表征。经实验发现，0.17g CuCl₂·2H₂O溶于10mL去离子水，0.025g明胶溶于10mL去离子水，二者混合，改变向混合液中加入NaOH溶液的不同浓度，或者改变向其中加入的还原剂抗坏血酸的量，在30℃下反应不同时间，60℃烘箱干燥所得样品中，加入0.066g抗坏血酸所得样品结晶度较好，产物纯度高，主要是Cu₂O，抗坏血酸加入量低于0.066g，产物中含有较多CuO，当抗坏血酸质量高于0.066g时，产物中有较多Cu，它们的光催化性能均好于加入抗坏血酸0.066g所得样品，说明Cu₂O中复合Cu和CuO有利于提高其光催化性能。NaOH对其光催化性能影响类似，但没有如此显著。

关键词：纳米Cu₂O/Cu与Cu₂O/CuO复合体系；液相还原法；光催化性能

Abstract

Human society after many industrial revolutions, especially since the Second Industrial Revolution, social productivity has never been improved, and the development of industrial agriculture has also brought great pollution problems. In these problems, organic pollutants in wastewater degradation of the problem is very prominent, these organic pollutants can not be natural degradation, the environment, especially the water environment is extremely harmful. At present, many domestic and international laboratories are seeking better means of degradation, by doping Cu₂O catalytic degradation of pollutants is one of the very popular areas.

Copper (I) Oxide, as a typical P-type semiconductor, has good photocatalytic performance, nano-grade cuprous oxide (Cu₂O) due to its unique physical and chemical properties, in the environment pollution treatment, energy conversion direction has a very important role.

Based on the high quantum recombination efficiency of single-phase semiconductors, the effect of high quantum recombination efficiency may be detrimental to the photocatalytic reaction. Cu₂O is modified by Cu and Cu₂O as additives. The Cu₂O / CuO and Cu₂O / CuO nano-grain, through the process of bio-mineralization, the introduction of biological macromolecules, in a relatively mild conditions to produce the required composite materials, Cu₂O / Cu composite materials preparation, photocatalytic degradation and other issues, and its catalytic mechanism is simple of the study, looking for better catalytic performance of the composite system.

In this paper, CuCl₂·2H₂O was used as the precursor solution, and the nano-grains with different morphologies and different particle sizes were synthesized by controlling the amount of L-ascorbic acid and NaOH. And its composition was analyzed by X - ray diffraction (XRD)，The grain size and morphology were analyzed by scanning electron microscopy (SEM), and the catalytic performance was characterized by photocatalytic performance test. It was found that 0.17 g of CuCl₂ • 2H₂O was dissolved in 10 mL of deionized water and 0.025 g of gelatin was dissolved in 10 mL of deionized water. The mixture was mixed to change the concentration of NaOH solution to the mixture, or to the reducing agent The amount of ascorbic acid was measured at 30 ° C for different times. The sample obtained by drying 0.06 g of ascorbic acid was better in the oven at 60 ° C. The product was of high purity, mainly Cu₂O, and ascorbic acid was less than 0.066 g, more CuO, when the ascorbic acid quality is higher than 0.066g, the products have more Cu, their photocatalytic performance is better than adding 0.066g ascorbic acid obtained samples, indicating Cu₂O in Cu and CuO is conducive to improving its photocatalytic performance. NaOH has a similar effect on its photocatalytic performance, but is not so significant.

Key Words: nano-Cu₂O / Cu and Cu₂O / CuO composite system; liquid phase reduction method; photocatalytic performance.

目录

摘要 I

目录 i

第1章 绪论 1

1.1纳米材料简介 1

1.2 Cu₂O纳米材料及其结构与性质 2

1.2.1 Cu₂O的化学性质 2

1.2.2 Cu₂O的晶体结构 2

1.2.3 Cu₂O的能带结构 3

1.3 Cu₂O的性能与其在工业生活中的应用 3

1.3.1 Cu₂O对有机污染物的光催化降解 3

1.3.2 Cu₂O在涂料方面的应用 4

1.3.3 Cu₂O在其他方面的应用 5

1.4 Cu₂O的制备方法 5

1.4.1 烧结法 5

1.4.2 化学沉淀法 5

1.4.3 水热合成法与溶剂热合成法 5

1.4.4 气相沉积法 6

1.4.5 溶胶-凝胶法（Sol-Gel） 6

1.5 Cu₂O纳米复合材料 6

1.5.1 常见Cu₂O的改性方法 6

1.5.1.1 Cu₂O与贵金属沉积 6

1.5.1.2 Cu₂O与其他氧化物复合 7

1.5.1.3 离子掺杂改性Cu₂O 7

1.6 Cu₂O的光催化机理 7

1.7 课题的主要研究意义、内容与创新点 8

第2章 实验试剂、仪器及样品表征方法 10

2.1 实验所用试剂 10

2.2 实验所用仪器 10

2.3 实验所用样品表征方法 11

2.3.1 X射线衍射（XRD）表征结构 11

2.3.2 扫描电子显微镜（SEM） 11

2.2.3 透射电子显微镜（TEM） 11

2.2.5紫外-可见分光光度计 12

第3章 Cu₂O/Cu和Cu₂O/CuO纳米复合体系的制备及表征分析 13

3.1 液相还原法绿色合成Cu₂O/Cu和Cu₂O/CuO纳米晶粒 13

3.2 Cu₂O/Cu和Cu₂O/CuO纳米复合体系的表征分析 13

3.2.1抗坏血酸加入量对 Cu₂O/Cu和Cu₂O/CuO纳米复合体系的影响 13

3.2.1.1 XRD衍射物相分析 13