磁性石墨烯复合材料制备与应用研究进展

doi:10.16085/j.issn.1000-6613.2021-0180

摘要/Abstract

摘要：

石墨烯具备多种优异的性能，但容易通过π-π堆积和范德华力作用产生聚集，重新堆叠成石墨。为了改善石墨烯的堆叠问题，提高石墨烯材料的应用性，越来越多的研究者将石墨烯及其衍生物和磁性纳米粒子复合，制备综合性能更优的新型材料。本文结合近年来国内外研究报道，总结了磁性石墨烯纳米复合材料的制备方法（水热/溶剂热、化学接枝法、微波辅助法等），概述了磁性石墨烯复合材料在环境样品分离富集、催化、涂层耐腐蚀性、吸波材料及能源等方面的应用，指出了目前磁性石墨烯复合材料研究中存在的一些问题，例如磁性颗粒容易发生团聚、生物安全性有待验证、氧化石墨烯的还原导致其表面吸附位点减少等。目前（氧化）石墨烯的制备工艺正在得到改善，而未来最重要的发展方向是加强对磁性石墨烯的表面改性，从而可使其表面具有更丰富的吸附位点，同时也可使石墨烯表面的磁性纳米粒子的形态及分布更均匀，更有利于稳定发挥磁性石墨烯的功能性。

关键词: 石墨烯, 磁性, 复合材料, 催化, 磁固相萃取

Abstract:

Graphene has a variety of excellent properties, however, it is easy to aggregate to restack into graphite by π-π stacking and van der Waals force. In order to solve the stacking problem and improve the applicability of graphene materials, graphene and its derivatives have been combined with magnetic nanoparticles to obtain new functional materials with high performance. Based on the recent internal and international research works, the preparation methods of magnetic graphene nanocomposites such as hydrothermal, solvothermal, chemical grafting and microwave-assisted methods are summarized. The application of magnetic graphene composite materials in the separation and enrichment of environmental samples, catalysis, corrosion resistance of coatings, wave-adsorbing material and energy area are introduced. Some problems of magnetic graphene composite materials, such as the tendency to agglomeration of magnetic particles, the verification of its biological safety and the reduction of adsorption sites led by graphene oxide reduction are pointed out. At present, the preparation technology of graphene (oxide) is improving and the most important research in the future is the surface modification of magnetic graphene, which can make the surface of graphene have more adsorption sites, and also lead to the more uniform morphology and distribution of magnetic nanoparticles on graphene surface, being conducive to the stable play of the functional properties of magnetic graphene.

Key words: graphene, magnetic, composites, catalysis, magnetic-solid phase extraction

中图分类号:

TB33

耿佳琦, 门园丽, 刘晨, 袁才登. 磁性石墨烯复合材料制备与应用研究进展[J]. 化工进展, 2022, 41(1): 277-285.

GENG Jiaqi, MEN Yuanli, LIU Chen, YUAN Caideng. Progress in preparation and application of magnetic graphene composites[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 277-285.

图/表 6

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制备方法	方法简介	优点	缺点	实例
直接磁化	在超声或振荡条件下直接通过物理吸附到石墨烯上	操作简单	不稳定、不能多次重复利用	采用静电自组装制备Fe₃O₄/GO纳米复合材料^［3］
水热法	以水为反应介质，在一定温度和压强条件下进行化学反应	污染小；纯度高、晶粒发育好、粒度分布窄、可控性好；团聚程度轻	无法观察晶体生长和材料合成的过程；温压控制较严格	采用水热法合成纳米杂化物MGZ@SiO，用作降解水中有机污染物的催化剂^［4］
溶剂热法	以有机溶剂为介质，在一定温度和压强条件下进行化学反应	绿色环保、成本低；磁性颗粒分散均匀，防止石墨烯团聚	温压控制严格；不太适合批量生产	利用溶剂法制备成磁性材料Fe₃O₄@N-rGO，用于提取饮料中的双酚内分泌干扰物^［5］
化学共沉淀法	磁力搅拌或超声辅助下，在石墨烯片层表面直接形成磁性纳米颗粒的沉积	可通过调节实验条件调节所生成复合物的形态、颗粒大小	磁性颗粒在石墨烯表面分散不均匀，有团聚的可能	通过化学共沉淀法制备磁性吸附剂，用于去除黄曲霉毒素^［6］
化学接枝法	先对磁性纳米粒子和石墨烯进行改性，再利用偶联剂和交联剂将二者通过化学键形式复合在一起	磁性石墨烯的稳定性较好	工艺复杂、产率低	将乙二胺接枝到磁性氧化石墨烯，制备DEA-GO@Fe₃O₄复合材料，研究多种因素对去除重金属废水中Cr（Ⅵ）的影响^［7］
微波辅助法	微波辐射可以为化学反应提供直接能量，加速化学反应进行	制备时间短；纳米颗粒细小、形状规则且分布均匀	对设备要求较高，存在安全隐患	通过微波辐射制备了Pd-CoFe₂O₄-GE三元复合纳米片，研究其对硼氢化钠还原4-硝基苯酚的催化性能^［8］
溶胶-凝胶法	以磁性金属盐或醇盐为前体，水解生成的活性单体吸附在石墨烯表面并聚合形成溶胶，进而形成凝胶	操作简单、设备低廉；磁性颗粒都键合在石墨烯的表面	工艺时间较长；原料较昂贵；所得到半成品制品容易产生开裂	采用溶胶-凝胶法制备rGO/TiO₂复合材料，并研究该材料的光催化性能^［9］

制备方法	方法简介	优点	缺点	实例
直接磁化	在超声或振荡条件下直接通过物理吸附到石墨烯上	操作简单	不稳定、不能多次重复利用	采用静电自组装制备Fe₃O₄/GO纳米复合材料^［3］
水热法	以水为反应介质，在一定温度和压强条件下进行化学反应	污染小；纯度高、晶粒发育好、粒度分布窄、可控性好；团聚程度轻	无法观察晶体生长和材料合成的过程；温压控制较严格	采用水热法合成纳米杂化物MGZ@SiO，用作降解水中有机污染物的催化剂^［4］
溶剂热法	以有机溶剂为介质，在一定温度和压强条件下进行化学反应	绿色环保、成本低；磁性颗粒分散均匀，防止石墨烯团聚	温压控制严格；不太适合批量生产	利用溶剂法制备成磁性材料Fe₃O₄@N-rGO，用于提取饮料中的双酚内分泌干扰物^［5］
化学共沉淀法	磁力搅拌或超声辅助下，在石墨烯片层表面直接形成磁性纳米颗粒的沉积	可通过调节实验条件调节所生成复合物的形态、颗粒大小	磁性颗粒在石墨烯表面分散不均匀，有团聚的可能	通过化学共沉淀法制备磁性吸附剂，用于去除黄曲霉毒素^［6］
化学接枝法	先对磁性纳米粒子和石墨烯进行改性，再利用偶联剂和交联剂将二者通过化学键形式复合在一起	磁性石墨烯的稳定性较好	工艺复杂、产率低	将乙二胺接枝到磁性氧化石墨烯，制备DEA-GO@Fe₃O₄复合材料，研究多种因素对去除重金属废水中Cr（Ⅵ）的影响^［7］
微波辅助法	微波辐射可以为化学反应提供直接能量，加速化学反应进行	制备时间短；纳米颗粒细小、形状规则且分布均匀	对设备要求较高，存在安全隐患	通过微波辐射制备了Pd-CoFe₂O₄-GE三元复合纳米片，研究其对硼氢化钠还原4-硝基苯酚的催化性能^［8］
溶胶-凝胶法	以磁性金属盐或醇盐为前体，水解生成的活性单体吸附在石墨烯表面并聚合形成溶胶，进而形成凝胶	操作简单、设备低廉；磁性颗粒都键合在石墨烯的表面	工艺时间较长；原料较昂贵；所得到半成品制品容易产生开裂	采用溶胶-凝胶法制备rGO/TiO₂复合材料，并研究该材料的光催化性能^［9］

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