论文总字数：24360字

摘 要

石墨烯由碳原子以六元环形式构成，是目前最薄的二维纳米材料，仅有单层碳原子的厚度，因此具有高导热性、高机械强度以及优良的电学性能等优点。而其一维形态碳纳米管长径比很大，轴向尺寸可达微米级，而径向尺寸仅为纳米级，也具有很高的机械强度。它们的出现为石墨烯基膜材料的研究提供了更多可能，在近年来受到了广泛关注。本文以石墨烯基纳滤膜的制备为目标，在多孔陶瓷支撑体表面采用一维二维碳材料构筑具有三维孔道结构的石墨烯基膜，其兼具陶瓷膜及纳米碳材料的优点。

采用往碳纳米管水分散液中加入适量嵌段共聚物F127和乙醇的方法，并借助超声分散，可以制得分散良好的碳纳米管分散液。采用L-抗坏血酸对氧化石墨烯进行还原，得到还原的氧化石墨烯。并将其与碳纳米管分散液混合，得到碳纳米管掺杂的石墨烯分散液。通过真空抽吸，利用石墨烯片在阳极氧化铝表面的层层自组装来制备多孔陶瓷支撑的石墨烯膜，并对制备好的膜层的微结构进行了表征。

将所有制备的石墨烯纳滤膜用于染料及腐殖酸分离过程的研究。在染料分离过程中，考察了石墨烯纳滤膜对不同种类染料的渗透性能和截留性能，研究发现，截留率均在97%以上，且渗透通量均维持在25-30 L·m^-2·h^-1·bar^-1之间；在腐殖酸分离过程中，考察了水回收率以及体积浓缩倍数的改变对石墨烯纳滤膜分离性能的影响，研究表明，在高水回收率以及高体积浓缩倍数下，石墨烯纳滤膜的渗透通量和截留率与初始相比均没有明显改变，截留率均在98%以上，渗透通量均保持在20 L·m^-2·h^-1·bar^-1左右，且重复操作十次后，膜性能无明显变化，膜的抗污染性及稳定性较好。

关键词：石墨烯 碳纳米管 嵌段共聚物 膜分离

ABSTRACT

Constituted by carbon atoms in the form of six-membered ring, graphene is so far the thinnest two-dimensional nanomaterials. Owing to its unique one-atom-thick structure, graphene exhibits prominent thermal, mechanical and electrical properties. As the one dimensional form of graphene, carbon nanotubes have long slenderness ratio, the axial size can reach micron grade, while the radial dimension can only reach nanoscale, as graphene, carbon nanotubes also exhibit excellent mechanical properties. The emergence of graphene and carbon nanotubes provides lots of possibilities for the research of membrane materials based on graphene, more and more researchers pay attention to them. This article aims at the preparation of membrane materials based on graphene, building a kind of membrane materials based on graphene with three-dimensional open-framework by one and two dimensional carbon materials on porous ceramic supports. It owns both advantages of ceramic membrane and carbon nano-materials.

By adding some block copolymer (F127) and ethanol into carbon nanotubes aqueous dispersion, and with the help of ultrasonic dispersion, finely dispersed carbon nanotubes aqueous dispersion was prepared. L ascorbic acid was introduced to reduce graphene oxide, thus obtaining reduced graphene oxide(rGO). Then mixed it with carbon nanotubes aqueous dispersion, carbon nanotubes/reduced graphene oxide aqueous dispersion was finally prepared. Vacuum assisted self-assembly technique was employed to prepare the graphene membrane with the support of porous ceramic membrane and characterized prepared membrane’s microstructure.

All the graphene membranes prepared would be used for dye separation and humic acid separation process. In dye separation process, water flux and rejection of graphene membranes for different dyes were studied, the results showed that rejection ratio of all dyes tested were above 97%, and permeation maintain 25-30 L·m^-2·h^-1·bar^-1. In humic acid separation process, the separation performance of graphene membranes with the changes of water recovery rate and volume concentration multiple was studied. The results showed that the water flux and rejection of graphene membranes reveal no obvious changes under the condition of high water recovery rate and large volume concentration multiple, the rejection ratio all above 98%, and permeation maintain around 20 L·m^-2·h^-1·bar^-1. Meanwhile, the membranes been operated ten times showed perfect anti-fouling performance and stability.

Keywords：graphene；carbon nanotube；block copolymer；membrane separation

目 录

摘 要 I

ABSTRACT II

第一章 文献综述 1

1.1 引言 1

1.2 石墨烯材料的制备方法 2

1.2.1 物理法制备石墨烯 2

1.2.2 化学法制备石墨烯 2

1.3 基于石墨烯材料的分离膜研究进展 3

1.3.1 基于石墨烯材料的液体分离膜研究进展 3

1.3.2 基于石墨烯材料的气体分离膜研究进展 4

1.3.3 基于石墨烯材料的膜分离机理 5

1.4 石墨烯的衍生形态及其应用 6

1.5 本文的研究思路与内容 7

第二章 碳纳米管掺杂的石墨烯材料的制备 8

2.1 实验试剂及仪器 8

2.2 碳纳米管材料的分散 9

2.2.1 分散剂的选择 10

2.2.2 P123和F127的对比 11

2.2.3 F127和CNTs的分散参数优化 15

2.2.4 混合溶剂的影响 17

2.3 氧化石墨烯还原制备石墨烯 18

2.4 碳纳米管与石墨烯材料的复合 21

2.5 本章小结 22

第三章 基于石墨烯材料无机纳滤膜的制备及表征 23

3.1 实验部分 23

3.1.1 实验试剂及仪器 23

3.1.2 真空抽吸成膜过程及装置 24

3.1.3 纳滤过程及装置 24

3.2 纳滤膜微结构的表征 25

3.3 纳滤膜性能的表征 26

3.4 纳滤膜应用于腐殖酸的分离 27

3.5 本章小结 31

第四章 结论与展望 32

4.1 结论 32

4.2 展望 33

参考文献 34

本科期间发表和撰写的论文与专利 36

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