GO-TiO_2改性PVDF复合膜去除微污染水体中氨氮
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摘要
以氧化石墨烯(GO)、二氧化钛(TiO_2)和氧化石墨烯-二氧化钛(GO-TiO_2)为改性物质,借助真空过滤法对聚偏氟乙烯(PVDF)微滤膜进行改性制备复合膜.利用接触角测量仪、扫描电子显微镜、傅里叶红外变换光谱、X射线粉末衍射仪等手段探究了复合膜的结构和亲水性.同时选用腐殖酸(HA)作为水中微污染物的代表考察了复合膜的抗污染性能.选择常州滆湖支浜水样作为原水,研究了复合膜在黑暗及紫外光条件下对氨氮的去除效果.结果表明,GO、TiO_2和GO-TiO_2(GT)复合膜均具有优于PVDF膜的亲水性和抗污染性能,黑暗条件下,GO浓度为1mg/mL的GO复合膜氨氮去除率最高,达到26.4%;紫外光条件下,GO和TiO_2间存在协同作用,GO-TiO_2浓度为1mg/mL、GO/TiO_2=3:1的GT复合膜氨氮去除效率达到最佳(58.2%).
The polyvinylidene fluoride(PVDF) microfiltration membrane was modified by vacuum filtration method with graphene oxide(GO), titanium dioxide(TiO_2) and graphene oxide-titanium dioxide(GO-TiO_2) as modifiers. The structure and hydrophilicity of the composite membranes were investigated by contact angle measurement, scanning electron microscopy(SEM), fourier transform infrared spectroscopy(FTIR) and X-ray diffraction(XRD). At the same time, humic acid(HA) was selected as the representative of micro-pollutants in water to examine the anti-pollution performance of the composite membrane. The removal efficiencies of ammonia nitrogen by composite membrane under dark and ultraviolet light conditions were studied by using the lake water samples from Gehu Lake branch in Changzhou as raw water. The results showed that GO, TiO_2 and GO-TiO_2(GT) composite membranes had better hydrophilicity and anti-pollution performance than PVDF membranes. Under dark condition, GO composite membrane with GO concentration of 1 mg/ml had the highest ammonia nitrogen removal rate(26.4%) under dark condition, while that of GT composite membrane with GO-TiO_2 concentration of 1 mg/mL and GO/TiO_2 =3:1 could reach the best(58.2%), for there was synergistic effect between GO and titanium dioxide under ultraviolet light.
The polyvinylidene fluoride(PVDF) microfiltration membrane was modified by vacuum filtration method with graphene oxide(GO), titanium dioxide(TiO_2) and graphene oxide-titanium dioxide(GO-TiO_2) as modifiers. The structure and hydrophilicity of the composite membranes were investigated by contact angle measurement, scanning electron microscopy(SEM), fourier transform infrared spectroscopy(FTIR) and X-ray diffraction(XRD). At the same time, humic acid(HA) was selected as the representative of micro-pollutants in water to examine the anti-pollution performance of the composite membrane. The removal efficiencies of ammonia nitrogen by composite membrane under dark and ultraviolet light conditions were studied by using the lake water samples from Gehu Lake branch in Changzhou as raw water. The results showed that GO, TiO_2 and GO-TiO_2(GT) composite membranes had better hydrophilicity and anti-pollution performance than PVDF membranes. Under dark condition, GO composite membrane with GO concentration of 1 mg/ml had the highest ammonia nitrogen removal rate(26.4%) under dark condition, while that of GT composite membrane with GO-TiO_2 concentration of 1 mg/mL and GO/TiO_2 =3:1 could reach the best(58.2%), for there was synergistic effect between GO and titanium dioxide under ultraviolet light.
引文
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[12]李明玉,赵倩,曾小龙,等.TiO2光电催化中光生电子降解对苯醌的行为研究[J].中国环境科学,2015,35(5):1397-1402.Li M Y,Zhao Q,Zeng X L,et al.The behaviors of photoinduced electrons on the degradation of the p-benzoquinone in TiO2 based photoelectrocatalytic process[J].China Environmental Science,2015,35(5):1397-1402.
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[16]Han J L,Xue X,Muhammad R H,et al.Functional graphene oxide membrane preparation for organics/inorganic salts mixture separation aiming at advanced treatment of refractory wastewater[J].Science of The Total Environment,2018,628:261-270.
[17]赵永军,李方,李佳峰,等.氧化石墨烯与纳米二氧化钛共混改性PES超滤膜的对比分析[J].膜科学与技术,2016,36(3):13-20.Zhao Y J,Li F,Li J F,et al.Comparative analysis of PES ultrafiltration membrane modified by graphene oxide and nano-titanium dioxide blend[J].Membrane Science and Technology,2016,36(3):13-20.
[18]Safarpour M,Vatanpour V,Khataee A,et al.Development of a novel high flux and foulingresistant thin film composite nanofiltration membrane by embedding reduced graphene oxide/TiO2[J].Separation and Purification Technology,2015,154:96-107.
[19]马志刚,马聪,王亮,等.GO-ZnO共混改性PVDF膜的制备及抗污染性能[J].中国给水排水,2018,34(1):42-47.Ma Z G,Ma C,Wang L,et al.Preparation and Antifouling Properties of GO/ZnO-blended PVDF Membrane[J].China Water&Wastewater,2018,34(1):42-47.
[20]Wang J,Wang Y M,Zhu J Y,et al.Construction of TiO2@graphene oxide incorporated antifoulingnanofiltration membrane with elevated filtration performance[J].Journal of Membrane Science,2017,533:279-288.
[21]Lou Y Y,Liu G P,Liu S N,et al.A facile way to prepare Ceramic supported graphene oxide composite membrane via silanegraft modification[J].Applied Surface Science,2014,307:631-637.
[22]Shao L,Cheng X Q,Wang Z X,et al.Tuning the performance of polypyrrole-based solvent-resistant composite nanofiltration membranes by optimizing poly-merization conditions and incorporating graphene oxide[J].Journal of Membrane Science,2014,452:82-89.
[23]Wu H T,Fan J,Liu E Z,et al.Facile hydrothermal synthesis of TiO2nanospindles reduced grapheneoxide composite with a enhanced photocatalytic activity[J].Journal of Alloys and Compounds,2015,623:298-303.
[24]Xu C,Cui A J,Xu Y L,et al.Graphene oxide-TiO2composite filtration membranes and their potential application for water purification[J].Carbon,2013,62:465-471.
[25]Shen J F,Yan B,Shi M,et al.One Step Hydrothermal synthesis of TiO2-reduced graphene oxide sheets[J].Journal of Materials Chemisty,2011,21:3415-3421.
[26]Zhu C Z,Guo S J,Wang P,et al.One-pot,Water-phase approach to high-quality graphene/TiO2composite nanosheets[J].Chemistry Community,2010,46:7148-7150.
[27]Zhou K F,Zhu Y H,Yang X L,et al.Preparation of graphene-TiO2composites with enhanced photocatalytic activity[J].New Journal of Chemistry,2011,35:353-359.
[28]Song X J,Zhou Q Z,Zhang T,et al.Pressure-assisted preparation of graphene oxide quantum dot-incorporated reverse osmosis membranes:antifouling and chlorine resistance potentials[J].Journal of Materials Chemisty A,2016,4:16896-16905.
[29]Hou C Y,Zhang Q H,Li Y G,et al.P25-Graphene hydrogels:Room-Temperature Synthesis and Application for Removal of methylene Blue from Aqueous Solution[J].Journal of Hazardous Materials,2012,205-206:229-235.
[30]Xu Z W,Zhang J G,Shan M J,et al.Organosilane-functionalized graphene oxide for enhanced antifouling andmechanical properties of polyvinylidene fluoride ultrafil-tration membranes[J].Journal of Membrane Science,2014,458:1-13.
[31]Hong J M,He Y.Effects of nano sized zinc oxide on the performance of PVDF microfiltration membranes[J].Desalination,2012,302:71-79.
[32]Camille P,Teresa J,Bandosz.Enhanced adsorption of ammonia on metalorganic framework/graphene oxide composites:Analysis of Surface Interactions[J].Advanced Functional Materials,2010,20:111-118.
[33]Wu C Z,Zhang X,Li C,et al.Adsorption of ammonium by graphene oxide-based composites prepared by UV irradiation and using as slow-release fertilizer[J].Journal of Polymers and the Environment,2018,26(12):4311-4320.
[34]Heng L,Meng L,L J Zhang,et al.Dipyridylbenzene as a charming sensitizer to significantly enhance the photocatalytic activity of titanium dioxide[J].Applied Catalysis B:Environmental,2018,232:472-480.
[35]Vesselin L,Dilyana T,Lubima B.Promoting the oxidative removal rate of2,4-dichlorophenoxyacetic acid on gold-doped WO3/Ti O2/reduced graphene oxide photocatalysts under UV light irradiation[J].Journal of Photochemistry and Photobiology A:Chemistry,2018,351:69-77.
[36]Lan X,Wang W L,Li Y S,et al.Graphene-containing composite Materials for water treatment[J].Progress in Chemistry,2013,25(0203):419-430.
[37]Chen W,Ye T,Xu H,et al.An ultrafiltration membrane with enhanced photocatalytic performance from grafted N-TiO2/graphene oxide[J].Royal Society of Chemistry,2017,7:9880-9887.
[38]Zhu C Y,Liu G G,Han K,et al.One-step facile synthesis of graphene oxide/TiO2composite as efficient photocatalytic membrane for water treatment:crossflow filtration operationand membrane fouling analysis[J].Chemical Engineering&Processing:Process Intensification,2017,120:20-26.
[2]王茜,郭晓燕,邵怀启,等.石墨烯及氧化石墨烯对分离膜改性的方法、效能和作用机理[J].化学进展,2015,27(10):1470-1480.Wang Q,Guo X Y,Shao H Q,et al.Methods,performances and mechanisms of separation membrane modified by graphene and graphene gxide[J].Progress in Chemistry,2015,27(10):1470-1480.
[3]李脆脆,王磊,李陈,等.SGO/PVDF-g-PSSA复合质子交换膜的制备及抗污染性研究[J].中国环境科学,2019,39(1):149-156.Li C C,Wang L,Li C,et al.Preparation and characterization of SGO/PVDF-g-PSSA composite proton exchange membrane and its anti-fouling properties[J].China Environmental Science,2019,39(1):149-156.
[4]Rabuni M F,Nik Sulaiman N M N,Aroua M K,et al.Effects of alkaline environments at mild conditions on the stability of PVDFmembrane:An experimental study[J].Industrial&Engineering Chemistry Research,2013,52(45):15874-15882.
[5]Liu F,Hashim N A,Liu Y,et al.Progress in the production and modification of PVDF membranes[J].Journal of Membrane Science,2011,375:1-27.
[6]Marcano D C,Kosynkin D V,Berlin J M,et al.Improved synthesis of graphene oxide[J].American Chemical Society Nano,2010,4(8):4806-4814.
[7]李翠霞,金海泽,谭高伟,等.rGO/TiO2复合光催化剂的制备及光催化性能[J].中国环境科学,2017,37(2):570-576.Li C X,Jing H Z,Tan G W,et al.The preparation and photocatalytic activity of rGO/TiO2composite photocatalyst[J].China Environmental Science,2017,37(2):570-576.
[8]韩燚.石墨烯纳滤膜的制备_改性及其性能研究[D].杭州:浙江大学,2014.Han Y.Preparation,modification and performance study of graphene nanofiltration menbrane[D].Hangzhou:Zhejiang University,2014.
[9]Zhang X,Wang Y,Liu Y F,et al.Prepar-ation,performances of PVDF/ZnO hybrid membranes and their applications in the removal of copper ions[J].Applied Surface Science,2014,316(15):333-340.
[10]Xia C S,Xu Z,Yu J,et al.Fabrication of microporous GO-TiO2membrane via an improved weak alkaline solgel method[J].Journal of Membrane Science,2018,561:10-18.
[11]刘立言,斐杨,龙明策,等.表面改性GOT/PVDF超滤膜的制备及对水中微污染物的去除[J].环境工程学报,2017,11(10):5381-5386.Liu L Y,Pei Y,Long M C,et al.Fabrication of surface modified GOT/PVDF ultrafiltration membrane and its removal of micropollutants from aqueous solution[J].Chinese Journal of Environmental Engineering,2017,11(10):5381-5386.
[12]李明玉,赵倩,曾小龙,等.TiO2光电催化中光生电子降解对苯醌的行为研究[J].中国环境科学,2015,35(5):1397-1402.Li M Y,Zhao Q,Zeng X L,et al.The behaviors of photoinduced electrons on the degradation of the p-benzoquinone in TiO2 based photoelectrocatalytic process[J].China Environmental Science,2015,35(5):1397-1402.
[13]冯雪婷,杨盛,文晨,等.Ag2CO3@PVDF/氧化石墨烯超滤膜及其分离性能[J].化工学报,2017,68(5):2169-2176.Feng X T,Yang S,Wen C,et al.Ag2CO3@PVDF/GO ultrafiltration membrane for water purification[J].Journal of Chemical Industry and Engineering,2017,68(5):2169-2176.
[14]Hu X B,Yua Y,Hou W M,et al.Effects of particle size and pH value on the hydrophilicity of graphene oxide[J].Applied Surface Science,2013,273:118-121.
[15]Long M C,Qin Y L,Chen C,et al.Origin of visible light photoactivity of reduced graphene oxide/TiO2 by in situ hydrothermal growth of undergrown TiO2 with graphene oxide[J].The Journal of Physical Chemistry C,2013,117:16734-16741.
[16]Han J L,Xue X,Muhammad R H,et al.Functional graphene oxide membrane preparation for organics/inorganic salts mixture separation aiming at advanced treatment of refractory wastewater[J].Science of The Total Environment,2018,628:261-270.
[17]赵永军,李方,李佳峰,等.氧化石墨烯与纳米二氧化钛共混改性PES超滤膜的对比分析[J].膜科学与技术,2016,36(3):13-20.Zhao Y J,Li F,Li J F,et al.Comparative analysis of PES ultrafiltration membrane modified by graphene oxide and nano-titanium dioxide blend[J].Membrane Science and Technology,2016,36(3):13-20.
[18]Safarpour M,Vatanpour V,Khataee A,et al.Development of a novel high flux and foulingresistant thin film composite nanofiltration membrane by embedding reduced graphene oxide/TiO2[J].Separation and Purification Technology,2015,154:96-107.
[19]马志刚,马聪,王亮,等.GO-ZnO共混改性PVDF膜的制备及抗污染性能[J].中国给水排水,2018,34(1):42-47.Ma Z G,Ma C,Wang L,et al.Preparation and Antifouling Properties of GO/ZnO-blended PVDF Membrane[J].China Water&Wastewater,2018,34(1):42-47.
[20]Wang J,Wang Y M,Zhu J Y,et al.Construction of TiO2@graphene oxide incorporated antifoulingnanofiltration membrane with elevated filtration performance[J].Journal of Membrane Science,2017,533:279-288.
[21]Lou Y Y,Liu G P,Liu S N,et al.A facile way to prepare Ceramic supported graphene oxide composite membrane via silanegraft modification[J].Applied Surface Science,2014,307:631-637.
[22]Shao L,Cheng X Q,Wang Z X,et al.Tuning the performance of polypyrrole-based solvent-resistant composite nanofiltration membranes by optimizing poly-merization conditions and incorporating graphene oxide[J].Journal of Membrane Science,2014,452:82-89.
[23]Wu H T,Fan J,Liu E Z,et al.Facile hydrothermal synthesis of TiO2nanospindles reduced grapheneoxide composite with a enhanced photocatalytic activity[J].Journal of Alloys and Compounds,2015,623:298-303.
[24]Xu C,Cui A J,Xu Y L,et al.Graphene oxide-TiO2composite filtration membranes and their potential application for water purification[J].Carbon,2013,62:465-471.
[25]Shen J F,Yan B,Shi M,et al.One Step Hydrothermal synthesis of TiO2-reduced graphene oxide sheets[J].Journal of Materials Chemisty,2011,21:3415-3421.
[26]Zhu C Z,Guo S J,Wang P,et al.One-pot,Water-phase approach to high-quality graphene/TiO2composite nanosheets[J].Chemistry Community,2010,46:7148-7150.
[27]Zhou K F,Zhu Y H,Yang X L,et al.Preparation of graphene-TiO2composites with enhanced photocatalytic activity[J].New Journal of Chemistry,2011,35:353-359.
[28]Song X J,Zhou Q Z,Zhang T,et al.Pressure-assisted preparation of graphene oxide quantum dot-incorporated reverse osmosis membranes:antifouling and chlorine resistance potentials[J].Journal of Materials Chemisty A,2016,4:16896-16905.
[29]Hou C Y,Zhang Q H,Li Y G,et al.P25-Graphene hydrogels:Room-Temperature Synthesis and Application for Removal of methylene Blue from Aqueous Solution[J].Journal of Hazardous Materials,2012,205-206:229-235.
[30]Xu Z W,Zhang J G,Shan M J,et al.Organosilane-functionalized graphene oxide for enhanced antifouling andmechanical properties of polyvinylidene fluoride ultrafil-tration membranes[J].Journal of Membrane Science,2014,458:1-13.
[31]Hong J M,He Y.Effects of nano sized zinc oxide on the performance of PVDF microfiltration membranes[J].Desalination,2012,302:71-79.
[32]Camille P,Teresa J,Bandosz.Enhanced adsorption of ammonia on metalorganic framework/graphene oxide composites:Analysis of Surface Interactions[J].Advanced Functional Materials,2010,20:111-118.
[33]Wu C Z,Zhang X,Li C,et al.Adsorption of ammonium by graphene oxide-based composites prepared by UV irradiation and using as slow-release fertilizer[J].Journal of Polymers and the Environment,2018,26(12):4311-4320.
[34]Heng L,Meng L,L J Zhang,et al.Dipyridylbenzene as a charming sensitizer to significantly enhance the photocatalytic activity of titanium dioxide[J].Applied Catalysis B:Environmental,2018,232:472-480.
[35]Vesselin L,Dilyana T,Lubima B.Promoting the oxidative removal rate of2,4-dichlorophenoxyacetic acid on gold-doped WO3/Ti O2/reduced graphene oxide photocatalysts under UV light irradiation[J].Journal of Photochemistry and Photobiology A:Chemistry,2018,351:69-77.
[36]Lan X,Wang W L,Li Y S,et al.Graphene-containing composite Materials for water treatment[J].Progress in Chemistry,2013,25(0203):419-430.
[37]Chen W,Ye T,Xu H,et al.An ultrafiltration membrane with enhanced photocatalytic performance from grafted N-TiO2/graphene oxide[J].Royal Society of Chemistry,2017,7:9880-9887.
[38]Zhu C Y,Liu G G,Han K,et al.One-step facile synthesis of graphene oxide/TiO2composite as efficient photocatalytic membrane for water treatment:crossflow filtration operationand membrane fouling analysis[J].Chemical Engineering&Processing:Process Intensification,2017,120:20-26.