二氧化钛纳米粒子-氧化石墨烯/聚酰亚胺混合基质膜的原位聚合及气体渗透性能

doi:10.7503/cjcu20160678

摘要/Abstract

摘要：

以钛酸四丁酯为前驱体, 采用浸渍-沉淀法制备二氧化钛纳米粒子-氧化石墨烯(TiO₂-GO)复合物, 再将TiO₂-GO复合物与4,4'-(六氟异亚丙基)邻苯二甲酸酐和4,4'-二氨基二苯醚通过原位聚合构建TiO₂-GO/TiO₂-GO/PI(聚酰亚胺)混合基质膜, 用于CO₂的渗透脱除. 采用傅里叶变换红外光谱(FTIR)、拉曼光谱(Raman)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、热失重(TG)和Zeta电位等表征了TiO₂-GO复合物和TiO₂-GO/PI混合基质膜的形貌与结构; 探讨了TiO₂掺杂量对TiO₂-GO复合物及TiO₂-GO/PI混合基质膜的结构和气体渗透性能的影响. 结果表明, TiO₂-GO复合物中TiO₂纳米粒子较均匀地沉积在GO片层上, TiO₂纳米粒子在形成的同时破坏了GO的结构, 使其无序度增加. TiO₂的掺杂对TiO₂-GO/PI混合基质膜的形貌与结构影响较小, 但提升了TiO₂-GO/PI混合基质膜的CO₂和N₂渗透性能. 但过量的掺杂使TiO₂粒子在GO片层上团聚, 从而导致TiO₂-GO复合物在混合基质膜中的分散性变差, CO₂渗透性及CO₂/N₂渗透选择性降低. 当TiO₂掺杂质量分数为30%时, TiO₂-GO/PI混合基质膜的CO₂渗透性为360 Barrer[1 Barrer=10^-10cm³(STP)·cm/(cm²·s·cm Hg)=7.5×10^-14cm³(STP)·cm/(cm²·s·Pa)], CO₂/N₂的渗透选择性可达31.

关键词: 二氧化钛纳米粒子-氧化石墨烯复合物, 聚酰亚胺, 混合基质膜, 原位聚合, 气体渗透性

Abstract:

Titanium dioxide-graphene oxide(TiO₂-GO) nanocomposites were synthesized by impregnation-reduction method using tetrabutyl titanate(C₁₆H₃₆O₄Ti) as the source of TiO₂, then TiO₂-GO/polyimide(TiO₂-GO/PI) mixed matrix membranes were fabricated via in-situ polymerization with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)/4,4'-oxydianiline(ODA)/TiO₂-GO. The structures of TiO₂-GO nanocomposites and TiO₂-GO/PI mixed matrix membranes were characterized by Fourier transform infrared spectroscopy(FTIR), Raman spectroscopy and transmission electron microscopy(TEM), scanning electron microscope(SEM), thermo-gravimetric analysis(TGA) and zeta potential instrument. The effects of TiO₂-doping on the structure of TiO₂-GO nanocomposites and TiO₂-GO/PI mixed matrix membranes were discussed, and the gas permeation properties of the mixed matrix membranes were measured. The results reveal that TiO₂ nanoparticles are impregnated uniformly in GO nanosheets, the dope of TiO₂ would slightly destroy the structure of GO, and the disorder degree of GO structure increased. But the dope of TiO₂ which was helpful to improve the dispersion of TiO₂-GO nanocomposite in the mixed matrix membrane, thus enhance the gas permeation properties of the mixed matrix membrane. However, the excess of TiO₂-doping would lead to the aggregation of TiO₂ particles on the GO surface, which depressed the gas permeation properties of the mixed matrix membrane. When the mass fraction of TiO₂-doping reached 15% in TiO₂-GO nanocomposite, the mixed matrix membrane demonstrated good CO₂ permeability and CO₂/N₂ permeation selectivity, and CO₂ permeability was 360 Barrer, and CO₂/N₂ permeation selectivity reached 31.

Key words: TiO2-graphene oxide nanocomposite, Polyimide, Mixed matrix membrane, In-situ polymerization, Gas permeation property

中图分类号:

O631

TrendMD:

杨彩虹, 满春利, 薛琬蕾, 王挺, 陈迪, 陈潜, 吴礼光. 二氧化钛纳米粒子-氧化石墨烯/聚酰亚胺混合基质膜的原位聚合及气体渗透性能. 高等学校化学学报, 2017, 38(4): 686.

YANG Caihong, MAN Chunli, XUE Wanlei, WANG Ting, CHEN Di, CHEN Qian, WU Liguang. Fabrication of TiO₂-GO/PI Mixed Matrix Membranes by In-situ Polymerization and Their Gas Permeation Property^†. Chem. J. Chinese Universities, 2017, 38(4): 686.

图/表 9

Fig.1 Schematic of gas permeation experimental setup1. H2; 2. CO2; 3. N2; 4. H2; 5. thermostatic water bath; 6. permeation cell; 7. soap-film flow-meter; 8. GC; 9. membrane; 10. porous metal disk; 11. O-ring(seal).

Fig.2 FTIR spectra of GO(a), TiO2-GO(Ⅰ)(b), TiO2-GO(Ⅱ)(c) and TiO2-GO(Ⅲ)(d) nanocomposites

Fig.3 Raman spectra of GO(a), TiO2-GO(Ⅰ)(b), TiO2-GO(Ⅱ)(c) and TiO2-GO(Ⅲ)(d) nanocomposites

Fig.4 TEM images of GO(A), TiO2 nanoparticles(B), TiO2-GO(Ⅰ)(C), TiO2-GO(Ⅱ)(D) and TiO2-GO(Ⅲ)(E) nanocomposites

Fig.5 Images of PI membrane(A), GO/PI nanocomposite(B), TiO2-GO/PI(Ⅰ)(C), TiO2-GO/PI(Ⅱ)(D) and TiO2-GO/PI(Ⅲ)(E) mixed matrix membranes

Fig.6 SEM images of GO/PI(A), TiO2-GO/PI(Ⅰ)(B), TiO2-GO/PI(Ⅱ)(C) and TiO2-GO/PI(Ⅲ)(D) mixed matrix membranes

Fig.7 Zeta potential and water contact angle of PI membrane(a), GO/PI nanocomposite(b), TiO2-GO/PI(Ⅰ)(c), TiO2-GO/PI(Ⅱ)(d) and TiO2-GO/PI(Ⅲ)(e) mixed matrix membranes

Fig.8 TGA of PI membrane(a), TiO2-GO/ PI(Ⅰ)(b), TiO2-GO/PI(Ⅱ)(c) and TiO2-GO/PI(Ⅲ)(d) mixed matrix membranes

Fig.9 CO2, N2 permeability and CO2/N2 permeation selectivity of PI member(a), GO/PI(b), TiO2-GO/PI(Ⅰ)(c), TiO2-GO/PI(Ⅱ)(d) and TiO2-GO/PI(Ⅲ)(e) mixed matrix membranes

参考文献 33

[1]	Bhown A. S., Freeman B. C., Environ. Sci. Technol., 2011, 4, 8624—8632
[2]	Scholes C. A., Stevens G. W., Kentish S. E., Fuel,2012, 96, 15—28
[3]	Zhang L. N., Cai K., Zhang F., Yue Q. F., Chem. Res. Chinese Universities, 2015, 31(1), 130—137
[4]	Bai H. P., Zheng Y. P., Li P. P., Zhang A. B., Chem. Res. Chinese Universities, 2015, 31(3), 484—488
[5]	Yang W. K., Liu F. F., Zhang E. S., Qiu X. P., Ji X. L., Chem. J. Chinese Universities, 2017, 38(1), 150—158
	(杨文轲, 刘芳芳, 张恩菘, 邱雪鹏, 姬相玲. 高等学校化学学报, 2017,38(1), 150—158)
[6]	Dong G. X., Li H. Y., Chen V., J. Mater. Chem. A, 2013, 1, 4610—4630
[7]	Zhao L., Chen Y. F., Wang T., Wu L. G., Acta Materiae Compositae Sinica, 2015, 31(3), 673—682
	(赵丽, 陈雨霏, 王挺, 吴礼光. 复合材料学报, 2015,31(3), 673—682)
[8]	Chen Y. F., Zhao L., Ding L. F., Wang T., Wu L. G., Chinese Journal of Inorganic Chemistry,2013, 30(10), 2301—2307
	(陈雨霏, 赵丽, 丁龙飞, 王挺, 吴礼光. 无机化学学报, 2013,30(10), 2301—2307)
[9]	Chen S. R., Xue M., Pan Y., Xu D., Qiu S. L., Chem. J. Chinese Universities, 2015, 36(5), 815—820
	(陈思如, 薛铭, 潘莹, 徐丹, 裘式纶. 高等学校化学学报, 2015,36(5), 815—820)
[10]	Beatriz Z., Carlos T., Joaquín C., Omoyemen E., Willianm J. K., AIChE J., 2015, 61(12), 4481—4490
[11]	Zachary P. S., Benny D. F., Angew. Chem. Int. Ed., 2014, 53, 10286—10288
[12]	Wang Q., Lyu M. Q., Zhang M., Yun J. H., Chen H. J., Wang L. Z., J. Phys. Chem. Lett., 2015, 6, 2806—2815
[13]	Liu G. P., Jin W. Q., Xu N. P., Chem. Soc. Rev., 2015, 44, 5016—5044
[14]	Xu H. H., Wang X. L., Chen R., Yu Z. Y., Chem. Res. Chinese Universities, 2014, 30(2), 205—210
[15]	Hu M., Mi B., Environ. Sci. Technol., 2013, 47, 3715—3723
[16]	Cheng C., Fabrication and Separation Property of Functional Graphene/Polyimide Hybrid Membranes, Zhejiang Gongshang University, Hangzhou, 2015
	(程诚. 功能化石墨烯/聚酰亚胺杂化膜构建及其分离性能研究, 杭州: 浙江工商大学, 2015)
[17]	Luo J., Wang F. H., Kong L. H., Zhang Y., Zhu H., Functional Materials, 2015, 46(7), 07100—07108
	(罗俊, 王芳辉, 孔令汉, 张瑶, 朱红. 功能材料, 2015,46(7), 07100—07108)
[18]	Xu C., Cui A., Xu Y., Fu X., Carbon,2013, 62, 465—471
[19]	Fei H. L., Dong J. C., Arellano-Jiménez M. J., Ye G. L., Kim D. N., Samuel E. L. G., Peng Z. W., Zhu Z., Qin F., Bao J. M., Yacaman M. J., Ajayan P. M., Chena D. L., Tourb J. M., Nature Commun., 2015, 6, 8668
[20]	Yu J. H., Fan M. G., Li B., Dong L. H., Zhang F. Y., Acta Phys. Chim. Sin., 2015, 31(3), 519—526
	(于建华, 范闽光, 李斌, 董丽辉, 张飞跃. 物理化学学报, 2015,31(3), 519—526)
[21]	Si Y. C., Samulski E. T., Chem. Mater., 2008, 20, 6792—6797
[22]	Kefayat U., Shu Y., Sun-Bok J., Zhu L., Cho K. Y., Oh W. C., Ultrason. Sonochem., 2014, 21(5), 1849—1857
[23]	Zhang X. X., Wu C. Z., Zhou J. F., Yang G. H., Liu Y. H., Zhang Y. W., Ding W. Z., Chem. J. Chinese Universities, 2015, 36(7), 1246—1253
	(张星星, 吴成章, 周建芳, 杨恭辉, 刘银河, 张玉文, 丁伟中. 高等学校化学学报, 2015,36(7), 1246—1253)
[24]	Sotto A., Boromand A., Zhang R. X., Luis P., Arsuaga J. M., Kim J., Bruggen B. V., J. Colloid Interface Sci., 2011, 363(2), 540—550
[25]	Yu S. L., Zuo X. T., Bao R. L., Xu X., Wang J., Xu J., Polymer,2009, 50(2), 553—559
[26]	Krishnamoorthy K., Mohan R., Kim S. J., Applied Physics Letters, 2011, 98(24), 244101-1—244101-3
[27]	Zhang Q., He Y. Q., Chen X. G., Hu D. H., Li L. J., Yin T., Ji L. L., Acta Physico-Chimica Sinica, 2010, 26(3), 654—662
	(张琼, 贺蕴秋, 陈小刚, 胡栋虎, 李林江, 尹婷, 季伶俐. 物理化学学报, 2010,26(3), 654—662)
[28]	Stankovich S., Dikin D. A., Piner R. D., Kohlhaas K. A., Kleinhammes A., Jia Y. Y., Wu Y., Nguyen S. B. T., Ruoff R. S., Carbon,2007, 45(7), 1558—1565
[29]	Shan M., Xue Q. Z., Jing N. N., Ling C. C., Zhang T., Yan Z. F., Zheng J. T., Nanoscale,2012, 4, 5477—5482
[30]	Ding M.X.,He T. B., Novel Polyimide Materials,Science Press, Beijing, 1998, 96—114
	(丁孟贤, 何天白. 聚酰亚胺新型材料, 北京: 科学出版社, 1998, 96—114)
[31]	Fu S. L., Sanders E. S., Kulkarni S. S., Wens G. B., Koros W. J., Carbon,2015, 95, 995—1006
[32]	Kammakakam I., Yoon H. W., Nam S. Y., Park H. B., J. Membr. Sci., 2015, 487, 90—98
[33]	Lu Y. H., Hao J. C., Li L., Song J., Fei M. Y., Xiao G. Y., Zhao H. B., Hu Z. Z., Wang T. H., Acta Polymerica Sinica, 2016, 8, 1145—1150
	(鲁云华, 郝继璨, 李琳, 宋晶, 费明月, 肖国勇, 赵洪斌, 胡知之, 王同华. 高分子学报, 2016, 8, 1145—1150)