SGO/PVDF-g-PSSA复合质子交换膜的制备及抗污染性研究
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摘要
为更好的提高PVDF-g-PSSA质子交换膜的性能,将磺化氧化石墨烯(SGO)与PVDF-g-PSSA共聚物混合制得SGO/PVDF-g-PSSA复合质子交换膜.用傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)以及X射线测定仪(XRD)证实了GO的成功磺化.对复合膜进行SEM表征并考察了复合膜的主要性能,得到了最佳SGO掺加量.使用耗散型石英晶体微天平(QCM-D)研究了复合膜的抗污染性能.实验结果表明:当SGO添加量为1.0%时,复合膜的含水率达到44.34%,质子传导率为0.085S/cm,综合性能达到最佳.QCM-D实验表明,在纯水和50mmol/LPBS条件下,复合膜表面的BSA吸附量均最低,且|ΔD/ΔF|最大,说明吸附层较为疏松,复合膜具有较好的抗污染性.
In order to improve the performance of PVDF-g-PSSA proton exchange membrane, SGO/PVDF-g-PSSA composite proton exchange membrane was prepared by mixing sulfonated graphene oxide(SGO) with PVDF-g-PSSA copolymer. Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS) and X-ray detector(XRD) were used to confirm the successful sulfonation of GO. The composite membrane was characterized by SEM and the main properties of the composite membranes were investigated. The optimal SGO dosing amount was obtained. The dissipative quartz crystal microbalance(QCM-D) was used to investigate the anti-fouling performance of the composite membranes. The results showed that when the SGO addition amount was 1.0%, the overall performance of composite membrane was optimized, the water content reached 44.34%, and the proton conductivity was 0.085S/cm. The QCM-D experiments showed that the BSA adsorption amount on the surface of the composite membrane was the lowest under pure water and 50mmol/L PBS, and |ΔD/ΔF| was the largest, indicating that the adsorption layer was loose and the composite membrane had better anti-fouling properties.
In order to improve the performance of PVDF-g-PSSA proton exchange membrane, SGO/PVDF-g-PSSA composite proton exchange membrane was prepared by mixing sulfonated graphene oxide(SGO) with PVDF-g-PSSA copolymer. Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS) and X-ray detector(XRD) were used to confirm the successful sulfonation of GO. The composite membrane was characterized by SEM and the main properties of the composite membranes were investigated. The optimal SGO dosing amount was obtained. The dissipative quartz crystal microbalance(QCM-D) was used to investigate the anti-fouling performance of the composite membranes. The results showed that when the SGO addition amount was 1.0%, the overall performance of composite membrane was optimized, the water content reached 44.34%, and the proton conductivity was 0.085S/cm. The QCM-D experiments showed that the BSA adsorption amount on the surface of the composite membrane was the lowest under pure water and 50mmol/L PBS, and |ΔD/ΔF| was the largest, indicating that the adsorption layer was loose and the composite membrane had better anti-fouling properties.
引文
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[24]Brunel D,Levesque P L,Ardiaca F,et al.Multiwalled carbon nanotube deposition on model environmental surfaces[J].Environmental Science&Technology,2013,47(18):10372.
[25]高哲,王磊,苗瑞,等.pH值对有机物(BSA)膜污染的影响[J].中国环境科学,2015,35(12):3640-3645.Gao Z,Wang L,Miao R,et al.Effect of pH on UF membrane fouling of organic foulant(BSA)[J].China Environmental Science,2015,35(12):3640-3645.Wang L,Miao R,Wang X,et al.Fouling behavior of typical organic foulants in polyvinylidene fluoride ultrafiltration membranes:characterization from microforces[J].Environmental Science&Technology,2013,47(8):3708-14.
[26]米娜,王磊,苗瑞,等.不同离子强度下蛋白质在PVDF膜面吸附行为评价[J].哈尔滨工业大学学报,2016,48(2):109-113.Mi N,Wang L,Miao R,et al.Evaluation on adsorption behaviour of protein on PVDF membrane surface under different ionic strengths[J].Journal of Harbin Institute of Technology,2016,48(2):109-113.
[2]Li W W,Yu H Q,He Z,et al.Towards sustainable wastewater treatment by using microbial fuel cells-centered technologies[J].Energy&Environmental Science,2014,7(3):911-924.
[3]Chae K J,Choi M,Ajayi F F,et al.Mass Transport through a Proton Exchange Membrane(Nafion)in Microbial Fuel Cells[J].Energy&Fuels,2008,22(1):169-176.
[4]Xu J,Sheng G P,Luo H W,et al.Fouling of proton exchange membrane(PEM)deteriorates the performance of microbial fuel cell[J].Water Research,2012,46(6):1817.
[5]颜明姣,王磊,李陈,等.臭氧预处理制备PVDF接枝SSS离子交换膜[J].环境工程学报,2016,10(11):6364-6370.Yan M J,Wang L,Li C,et al.Preparation of PVDF grafted SSS ion exchange membrane by ozone pretreatment[J].Chinese Journal Environmenta Engineeringl,2016,10(11):6364-6370.
[6]Zhu Z,Wang L,Xu Y,et al.Preparation and characteristics of graphene oxide-blending PVDF nanohybrid membranes and their applications for hazardous dye adsorption and rejection[J].Journal of Colloid&Interface Science,2017,504:429.
[7]施奕磊,杨腊文,蒋仲庆,等.氧化石墨烯在质子交换膜中的应用研究进展[J].膜科学与技术,2015,35(5):114-121.Shi Y L,Yang L W,Jiang Z Q,et al.Recent progress in graphene oxide applied for proton exchange membrane fuel cells[J].Membrane Science and Technology,2015,35(5):114-121.
[8]Chien H C,Tsai L D,Huang C P,et al.Sulfonated graphene oxide/Nafion composite membranes for high-performance direct methanol fuel cells[J].International Journal of Hydrogen Energy,2013,38(31):13792-13801.
[9]Beydaghi H,Javanbakht M,Kowsari E.Synthesis and characterization of poly(vinyl alcohol)/sulfonated graphene oxide nanocomposite membranes for use in proton exchange membrane fuel cells(PEMFCs)[J].Industrial&Engineering Chemistry Research,2014,53(43):16621-16632.
[10]Ayyaru S,Ahn Y H.Application of sulfonic acid group functionalized graphene oxide to improve hydrophilicity,permeability,and antifouling of PVDF nanocomposite ultrafiltration membranes[J].Journal of Membrane Science,2017,525:210-219.
[11]王磊,张全,李陈,等.PVDF/TiO2-g-PSSA复合质子交换膜的制备及抗污染性研究[J].膜科学与技术,2017,37(3):74-80.Wang L,Zhang Q,Li C,et al.Preparation of PVDF/TiO2-g-PSSAmodified proton exchange membrane and evaluation on its anti-fouling characteristics[J].Membrane Science and Technology,2017,37(3):74-80.
[12]王磊,黄松,黄丹曦,等.QCM-D研究BSA在不同改性PVDF超滤膜表面的吸附行为[J].哈尔滨工业大学学报,2016,48(8):78-83.Wang L,Huang S,Huang D X,et al.Adsorption behaviors of BSA on different modified PVDF ultrafiltration membranes using QCM-D[J].Journal of Harbin Institute of Technology,2016,48(8):78-83.
[13]Li C,Wang L,Wang X,et al.Synthesis of PVDF-g-PSSA proton exchange membrane by ozone-induced graft copolymerization and its application in microbial fuel cells[J].Journal of Membrane Science,2017,527:35-42.
[14]薛艳红,傅荣强,徐铜文,等.磺化聚醚醚酮与壳聚糖共混制备直接甲醇燃料电池用质子交换膜[J].高分子学报,2010,(3):285-291.Xue Y H,Fu R Q,Xu T W,et al.Preparation of speek and SPEEK/Chitosan composite proton-exchange membranes for application in direct methanol fuel cells[J].Acta Poiymerica Sinica,2010,(3):285-291.
[15]Wu L,Xu T,Wu D,et al.Preparation and characterization of CPPO/BPPO blend membranes for potential application in alkaline direct methanol fuel cell[J].Journal of Membrane Science,2008,310(1):577-585.
[16]程顺喜,马文石.磺化聚醚醚酮/氧化石墨复合膜的制备与表征[J].合成材料老化与应用,2009,38(3):28-31.Cheng S X,Man W S.Preparation and characterization of sulfonated poly(ether ether ketone)/graphite oxide composite membranes[J].Synthetic Materials Aging and Application,2009,38(3):28-31.
[17]祝振鑫.膜材料的亲水性、膜表面对水的湿润性和水接触角的关系[J].膜科学与技术,2014,34(2):1-4.Zhu Z X.Hydrophilicity,wettability and contact angle[J].Membrane Science and Technology,2014,34(2):1-4.
[18]马宁,蔡芳昌,殷浩,等.交流阻抗法测试质子交换膜电导率的影响因素[J].高分子材料科学与工程,2012,(11):125-128.Ma N,Cai F C,Yin H,et al.Effect factors of PEM conductivity measurement by impedance spectroscopy[J].Polymer Materials Science&Engineering,2012,(11):125-128.
[19]郭长春.氧化石墨烯(GO)与磺化氧化石墨烯(SGO)的制备及其修饰电极电化学研究[D].青岛:青岛大学,2012.Guo C C.Preparation of graphene Oxide(GO)and sulfonated graphene oxide(SGO)and electrochemical research of its modified electrode[D].Qingdao:Qingdao University,2012.
[20]毕朝刚.氧化石墨烯及其复合物的制备与表征[D].大连:大连理工大学,2014.Bi Z G.Synthesis and characterization of graphene oxides and their composites[D].Dalian:Dalian University of Technology,2014.
[21]Gahlot S,Sharma P P,Kulshrestha V,et al.SGO/SPES-based highly conducting polymer electrolyte membranes for fuel cell application[J].Acs Appl Mater Interfaces,2014,6(8):5595-5601.
[22]Quevedo I R,Tufenkji N.Influence of solution chemistry on the deposition and detachment kinetics of a CdTe quantum dot examined using a quartz crystal microbalance[J].Environmental Science&Technology,2009,43(9):3176-82.
[23]王磊,朱苗,苗瑞,等.典型一价阳离子对蛋白质膜污染的影响特性[J].中国环境科学,2017,37(5):1792-1797.Wang L,Zhu M,Miao R,et al.Effect of monovalent cations on ultrafiltration membrane fouling of protein[J].China Environmental Science,2017,37(5):1792-1797.
[24]Brunel D,Levesque P L,Ardiaca F,et al.Multiwalled carbon nanotube deposition on model environmental surfaces[J].Environmental Science&Technology,2013,47(18):10372.
[25]高哲,王磊,苗瑞,等.pH值对有机物(BSA)膜污染的影响[J].中国环境科学,2015,35(12):3640-3645.Gao Z,Wang L,Miao R,et al.Effect of pH on UF membrane fouling of organic foulant(BSA)[J].China Environmental Science,2015,35(12):3640-3645.Wang L,Miao R,Wang X,et al.Fouling behavior of typical organic foulants in polyvinylidene fluoride ultrafiltration membranes:characterization from microforces[J].Environmental Science&Technology,2013,47(8):3708-14.
[26]米娜,王磊,苗瑞,等.不同离子强度下蛋白质在PVDF膜面吸附行为评价[J].哈尔滨工业大学学报,2016,48(2):109-113.Mi N,Wang L,Miao R,et al.Evaluation on adsorption behaviour of protein on PVDF membrane surface under different ionic strengths[J].Journal of Harbin Institute of Technology,2016,48(2):109-113.