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高渗透性石墨烯杂化炭膜的制备及表征

作者：张兵¹，周佳玲¹，吴永红¹，李琳²，王同华²

单位： 1沈阳工业大学石油化工学院，辽宁辽阳 111003；2大连理工大学化工学院，精细化工国家重点实验室，辽宁大连 116024

关键词：聚酰亚胺；炭膜；石墨烯；渗透性

DOI号：

分类号： TQ028.8

出版年,卷(期):页码： 2016,36(2):7-12

摘要：

以4, 4'-二氨基二苯醚-3, 3', 4, 4'-二苯甲酮四酸二酐（BTDA-ODA）型聚酰亚胺为前驱体，石墨烯为掺杂剂，经共混、成膜、干燥和热解过程制备了杂化炭膜。采用热失重、扫描电镜、X射线衍射、红外光谱及渗透等技术分别对前驱体热稳定性、炭膜微观形貌、微观结构、表面基团和气体分离性能进行了分析。考察了石墨烯含量对炭膜微结构与性能的影响。结果显示，引入石墨烯使前驱体热稳定性提高；石墨烯与炭膜母体间兼容性良好，在大幅度提高气体渗透性同时保持了较好的分子筛分能力；掺杂石墨烯后，使炭膜对H2，CO2与O2的渗透性分别提高了6.8倍，46倍和59倍。当石墨烯用量为0.5%时，杂化炭膜对CO2渗透性达1236.7 Barrer，此时CO2/N2选择性达24.1，具有较好的应用前景。

Hybrid carbon membranes were prepared by using 4, 4'-diaminodiphenyl ether -3, 3 ', 4, 4'-benzophenone tetracarboxylic dianhydride (BTDA-ODA) polyimide as precursor ang graphene as dopant, via the processes of blending, membrane-forming, drying and pyrolysis. The TG, SEM, XRD, IR and gas permeation technique were respectively applied to characterize the thermal stability of precursor, and the morphology, microstructure, surface chemical moieties and separation performance of carbon membranes. The effects of graphene content on the microstructure and properties of carbon membrane were investigated. Results show that the introduction of graphene leads to the enhancement of thermal stability of precursors. The resultant hybrid carbon membranes have both excellent permeability and molecular sieving ability due to the fairly well compatibility between graphene and membrane matrix. The gas permeability of hybrid carbon membranes is respectively increased by 6.8 times for H2, 46 times for CO2 and 59 times for O2. When the amount of graphene is 0.5%, the hybrid carbon membranes reveal attractive gas separation performance commercially, i.e., CO2 permeability of 1236.7 Barrer and CO2/N2 selectivity of 24.1.

基金项目：

国家自然科学基金（20906063，21436009，21276035，21376037，21576035，21506020），辽宁省自然科学基金（20102170），辽宁省高校杰出青年学者培养计划项目（LJQ2012010），中国博士后第56批科学基金（2014M561232）和精细化工国家重点实验室开放基金（KF1107）。

作者简介：

张兵（1977－），男，辽宁辽阳人，博士，教授，主要从事气体分离炭膜的制备与应用基础研究. *通讯作者，E-mails: bzhangdut@163.com, wangth@dlut.edu.cn.

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