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氧化石墨烯(GO)膜具有层状亚纳米通道,适用于尺寸依赖的污染物分子筛分;其中,通过交联来稳定层间距是防止其溶胀、保障其对目标污染物去除的重要途径之一。乙二胺是常用的交联剂,但乙二胺改性后氧化石墨烯膜表面亲水性变弱、水通量降低。本研究通过碱化的方式,将氧化石墨烯膜边缘经乙二胺改性后形成的酰胺结构以及未反应的羧基转化为亲水性更强的羧酸根离子,促进水分子进入层间通道,从而大幅度提高了膜的亲水性。碱化后的乙二胺功能化氧化石墨烯膜(rbGO/PVDF)瞬间水接触角从(59±1.3)°减小到(17±0.2)°,亲水性显著提高;FT-IR与XPS分析表明,rbGO/PVDF膜中羧酸根离子(―COO~-)含量从0.8%增加至7.6%,乙二胺与羧基形成的酰胺结构被破坏;相应的,碱化后的膜水通量高达(307.0±11.0)L/(m2·h),是碱化前的44倍。以络合态重金属Cu-EDTA2-为目标污染物,rbGO/PVDF膜展现出较高的去除能力,具有深度去除工业废水中重金属络合物的潜力。
Abstract：Graphene oxide(GO) membranes with layered sub-nanochannels are ideal 2D materials for size-dependent molecular screening. The crosslinking strategy is one of key approaches to stabilize layer spacing to prevent membrane swelling and ensure the removal of the target contaminants. Ethylene diamine(EDA), commonly used as the cross-linking agent for GO membrane modification, always decreases the surface hydrophilicity and water flux. In this study, alkalinization was utilized to convert the amide structure(formed by EDA modification)at the edge of graphene oxide membranes along with unreacted carboxyl groups into more hydrophilic carboxylate ions, which was proved to be efficient in promoting water molecules entering the interlayer channels and thus improving the hydrophilicity of GO membranes. The water contact angle of alkalinized EDA-functionalized graphene oxide membrane(rbGO/PVDF)decreased from(59±1.3)° to(17±0.2)°, indicating the significantly improved hydrophilicity of rbGO/PVDF membrane. In addition, FT-IR and XPS characterizations both demonstrated the carboxylate ion(―COO~-) contents in the rbGO/PVDF membrane increased from 0.8% to 7.6%,suggesting the destruction of amide structure. A fast and selective water permeation was observed through separation of Cu-EDTA2-from water, with the permeance of(307.0±11.0)L/(m2·h),nearly 44 times higher than that of the control pristine GO membranes, suggesting the great potential in deep removal of heavy metal complexes in industrial wastewater.
[1]Nair R R,Wu H A,Jayaram P N,Grigorieva I V,Geim A K.Unimpeded permeation of water through helium-leak-tight graphene-based membranes[J].Science,2012,335(6067):442-444.
[2]Hummer G,Rasaiah J C,Noworyta J P.Water conduction through the hydrophobic channel of a carbon nanotube[J].Nature,2001,414(6860):188-190.
[3]Kim Hyo Won,Yoon Hee Wook,Yoon Seon Mi,Yoo Byung Min,Ahn Byung Kook,Cho Young Hoon,Shin Hye Jin,Yang Hoichang,Paik Ungyu,Kwon Soongeun,Choi Jae Young,Park Ho Bum.Selective gas transport through few-layered graphene and graphene oxide membranes[J].Science,2013,342(6154):91-95.
[4]Li Hang,Song Zhuonan,Zhang Xiaojie,Huang Yi,Li Shiguang,Mao Yating,Ploehn Harry J,Bao Yu,Yu Miao.Ultrathin,molecular-sieving graphene oxide membranes for selective hydrogen separation[J].Science,2013,342(6154):95-98.
[5]Chen Jing Jing,Meng Jie,Zhou Yang Bo,Wu Han Chun,Bie Ya Qing,Liao Zhi Min,Yu Da Peng.Layer-by-layer assembly of vertically conducting graphene devices[J].Nature Communications,2013,4(1):1921.
[6]韩硕,王磊,孟晓荣,黄丹曦.氧化石墨烯改性PVDF超滤膜截留染料性能研究[J].水处理技术,2018,44(11):50-54.
[7]田隆,刘婷,孙克宁.用于水质净化的氧化石墨烯膜研究进展[J].化工学报,2020,71(9):4112-4130.
[8]Werber Jay R,Osuji Chinedum O,Elimelech Menachem.Materials for next-generation desalination and water purification membranes[J].Nature Reviews Materials,2016,1(5):Art no 16018.
[9]Fang Ming,Zhang Zhen,Li Jianfeng,Zhang Hongdong,Lu Hongbin,Yang Yuliang.Constructing hierarchically structured interphases for strong and tough epoxy nanocomposites by amine-rich graphene surfaces[J].Journal of Materials Chemistry,2010,20(43):9635-9643.
[10]Stankovich Sasha,Dikin Dmitriy A,Compton Owen C,Dommett Geoffrey H B,Ruoff Rodney S,Nguyen Sonbinh T.Systematic post-assembly modification of graphene oxide paper with primary alkylamines[J].Chemistry of Materials,2010,22(14):4153-4157.
[11]Zhu Yu,Higginbotham Amanda L,Tour James M.Covalent functionalization of surfactantwrapped graphene nanoribbons[J].Chemistry of Materials,2009,21(21):5284-5291.
[12]Bourlinos Athanasios B,Gournis Dimitrios,Petridis Dimitrios,SzabóTamás,Szeri Anna,Dékány Imre.Graphite oxide:Chemical reduction to graphite and surface modification with primary aliphatic amines and amino acids[J].Langmuir,2003,19(15):6050-6055.
[13]Hung Wei Song,Tsou Chi Hui,De Guzman Manuel,An Quan Fu,Liu Ying Ling,Zhang Ya Ming,Hu Chien Chieh,Lee Kueir Rarn,Lai Juin Yih.Cross-linking with diamine monomers to prepare composite graphene oxide-framework membranes with varying dspacing[J].Chemistry of Materials,2014,26(9):2983-2990.
[14]Kim Nam Hoon,Kuila Tapas,Lee Joong Hee.Simultaneous reduction,functionalization and stitching of graphene oxide with ethylenediamine for composites application[J].Journal of Materials Chemistry A,2013,1(4):1349-1358.
[15]Ma Hui Ling,Zhang Youwei,Hu Qi Hui,Yan Dong,Yu Zhong Zhen,Zhai Maolin.Chemical reduction and removal of Cr(VI) from acidic aqueous solution by ethylenediamine-reduced graphene oxide[J].Journal of Materials Chemistry,2012,22(13):5914.
[16]Kovtyukhova Nina I,Ollivier Patricia J,Martin Benjamin R,Mallouk Thomas E,Chizhik Sergey A,Buzaneva Eugenia V,Gorchinskiy Alexandr D.Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations[J].Chemistry of Materials,1999,11(3):771-778.
[17]Lerf Anton,He Heyong,Forster Michael,Klinowski Jacek.Structure of graphite oxide revisited[J].The Journal of Physical Chemistry B,1998,102(23):4477-4482.
[18]Wang Jianqiang,Zhang Pan,Liang Bin,Liu Yuxuan,Xu Tao,Wang Lifang,Cao Bing,Pan Kai.Graphene oxide as an effective barrier on a porous nanofibrous membrane for water treatment[J].ACS Applied Materials&Interfaces,2016,8(9):6211-6218.
[19]Zhang Wenbing,Shi Mengqi,Heng Zhongxuan,Zhang Weiming,Pan Bincai.Soft particles enable fast and selective water transport through graphene oxide membranes[J].Nano Letters,2020,20(10):7327-7332.
[20]Wang Zenglin,Furuya Akihiko,Yasuda Keiichirou,Ikeda Hideo,Baba Tomoyuki,Hagiwara Muneaki,Toki Sotaro,Shingubara Shoso,Kubota Hiroshi,Ohmi Tadahiro.Adhesion improvement of electroless copper to a polyimide film substrate by combining surface microroughening and imide ring cleavage[J].Journal of Adhesion Science and Technology,2002,16(8):1027-1040.
[21]Thebo Khalid Hussain,Qian Xitang,Zhang Qing,Chen Long,Cheng Huiming,Ren Wencai.Highly stable graphene-oxide-based membranes with superior permeability[J].Nature Communications,2018,9(1):1486.
[22]Lee Haeshin,Dellatore Shara M,Miller William M,Messersmith Phillip B.Musselinspired surface chemistry for multifunctional coatings[J].Science,2007,318(5849):426-430.
[23]Xu Weiwei,Fang Chao,Zhou Fanglei,Song Zhuonan,Liu Qiuli,Qiao Rui,Yu Miao.Selfassembly:A facile way of forming ultrathin,high-performance graphene oxide membranes for water purification[J].Nano Letters,2017,17(5):2928-2933.
[24]Zhang Yongzhi,Su Kunmei,Li Zhenhuan.Graphene oxide composite membranes crosslinked with urea for enhanced desalting properties[J].Journal of Membrane Science,2018,563:718-725.
[25]An Di,Yang Ling,Wang Tingjie,Liu Boyang.Separation performance of graphene oxide membrane in aqueous solution[J].Industrial&Engineering Chemistry Research,2016,55(17):4803-4810.
基本信息:
DOI：10.16026/j.cnki.iea.2022030205
中图分类号:X703;TQ051.893
引用信息:
[1]雷丝雨,张文彬,张炜铭.碱化反应对乙二胺功能化氧化石墨烯纳滤膜离子分离效率的提升研究[J].离子交换与吸附,2022,38(03):205-216.DOI:10.16026/j.cnki.iea.2022030205.
基金信息:
国家重点研发计划(2021YFA1201703)
2022-06-20
2022-06-20