泡沫镍负载Fe_2O_3/α-MoO_3可见光催化降解水中铜绿微囊藻
|
摘要
采用共沉积法合成不同配比的Fe_2O_3/α-MoO_3复合光催化剂,利用X射线衍射(XRD)、扫描电子显微镜(SEM)及紫外-可见漫反射光谱(UV-Vis DRS)等技术分析其晶体结构、形貌及其光学性能,以铜绿微囊藻(Microcystis aeruginosa,MA)为污染物模型,通过检测叶绿素a、丙二醛、可溶性蛋白含量的变化,研究该催化剂在可见光(λ≥420nm)照射下催化降解MA的性能。结果表明:当Fe_2O_3质量为α-MoO_3质量的1.0%时,复合催化剂1.0%Fe_2O_3/α-MoO_3对MA的催化降解效率最佳;pH 7.5条件下,1.0%Fe_2O_3/α-MoO_3用量为0.4g/L时,可见光照射5h后MA的去除率达96%,藻细胞溶出的可溶性蛋白量最低;1.0%Fe_2O_3/α-MoO_3在可见光照射下除藻过程中产生的丙二醛产量较避光反应时明显增多。将1.0%Fe_2O_3/α-MoO_3负载到泡沫镍后,表现出良好的稳定性和循环利用性,对实际水体中的混合藻类达到90%以上的降解率。
Fe_2O_3/α-MoO_3 composite photocatalysts with different ratios were synthesized by co-deposition method.Their crystal structure,morphology and optical performance were analyzed by means of X-ray diffraction(XRD),scanning electron microscopy(SEM)and ultraviolet visible diffuse reflectance spectroscopy(UV-Vis DRS),etc.Microcystis aeruginosa(MA)was used as the model pollutant to study the catalytic degradation of MA under visible light irradiation(λ≥420nm)by detecting the changes of chlorophyll a,malondialdehyde and soluble protein content.The results show that the removal efficiency of MA is the highest with the mass ratio of Fe_2O_3toα-MoO_3 at 1∶100(1.0%);At pH =7.5,when the dosage of 1.0% Fe_2O_3/a-MoO_3 is 0.4g/L,the removal rate of MA reaches 96%after 5hours of visible light irradiation,and the soluble protein content of algae cells is the lowest.The malondialde-hyde production of 1.0% Fe_2O_3/α-MoO_3 during algae removal under visible light irradiation is significantly higher than that during dark reaction.When Fe_2O_3/α-MoO_3 is loaded onto foam nickel,it shows good stability and recycling efficiency,and the degradation rate of mixed algae in water sample is more than 90%.
Fe_2O_3/α-MoO_3 composite photocatalysts with different ratios were synthesized by co-deposition method.Their crystal structure,morphology and optical performance were analyzed by means of X-ray diffraction(XRD),scanning electron microscopy(SEM)and ultraviolet visible diffuse reflectance spectroscopy(UV-Vis DRS),etc.Microcystis aeruginosa(MA)was used as the model pollutant to study the catalytic degradation of MA under visible light irradiation(λ≥420nm)by detecting the changes of chlorophyll a,malondialdehyde and soluble protein content.The results show that the removal efficiency of MA is the highest with the mass ratio of Fe_2O_3toα-MoO_3 at 1∶100(1.0%);At pH =7.5,when the dosage of 1.0% Fe_2O_3/a-MoO_3 is 0.4g/L,the removal rate of MA reaches 96%after 5hours of visible light irradiation,and the soluble protein content of algae cells is the lowest.The malondialde-hyde production of 1.0% Fe_2O_3/α-MoO_3 during algae removal under visible light irradiation is significantly higher than that during dark reaction.When Fe_2O_3/α-MoO_3 is loaded onto foam nickel,it shows good stability and recycling efficiency,and the degradation rate of mixed algae in water sample is more than 90%.
引文
[1] WU Y H,HE J Z,YANG L Z.Evaluating adsorption and biodegradation mechanisms during the removal of Microcystin-RR by periphyton[J].Environmental Science&Technology,2010,44(16):6319-6324.DOI:10.1021/es903761y.
[2] HYENSTRAND P,ROHRLACK T,BEATTIE K,et al.Laboratory studies of dissolved radiolabelled Microcystin-LR in lake water[J].Water Research,2003,37(14):3299-3306.DOI:10.1016/S0043-1354(03)00180-5.
[3] GU N,GAO J L,LI H,et al.Montmorillonite-supported with Cu2O nanoparticles for damage and removal of Microcystis aeruginosa under visible light[J].Applied Clay Science,2016,132-133:79-89.DOI:10.1016/j.clay.2016.05.017.
[4] YU X J,ZHOU J Y,WANG Z P,et al.Medium optimisation for improved growth-rate inhibition of Microcystis aeruginosa exposed to AgBiO3 using response-surface methodology[J].Advanced Materials Research,2011,255-260:2940-2948.DOI:10.4028/www.scientific.net/AMR.255-260.2940.
[5] SONG J K,WANG X J,MA J X,et al.Visible-lightdriven in situ inactivation of Microcystis aeruginosa with the use of floating g-C3N4 heterojunction photocatalyst:Performance,mechanisms and implications[J].Applied Catalysis B Environmental,2018,226(15):83-92.DOI:10.1016/j.apcatb.2017.12.034.
[6] ZHANG G Y,FENG Y,XU Y Y,et al.Controlled synthesis of mesoporousα-Fe2O3nanorods and visible light photocatalytic property[J].Materials Research Bulletin,2012,47(3):625-630.DOI:10.1016/j.materresbull.2011.12.032.
[7] WANG Y M,YU T,CHEN X Y,et al.Enhancement of photoelectric conversion properties of SrTiO3/α-Fe2O3 heterojunction photoanode[J].Journal of Physics D Applied Physics,2007,40(13):3925-3930.DOI:10.1088/0022-3727/40/13/003.
[8]甄延忠,王杰,王丹军,等.一维Fe2O3/α-MoO3异质结的制备及其可见光光催化性能[J].人工晶体学报,2017,46(1):55-62.DOI:10.16553/j.cnki.issn1000-985x.2017.01.010.ZHEN Y Z,WANG J,WANG D J,et al.Preparation and visible-light photocatalytic properties of one dimensional Fe2O3/α-MoO3heterostructures[J].Journal of Synthetic Crystals,2017,46(1):55-62.DOI:10.16553/j.cnki.issn1000-985x.2017.01.010(Ch).
[9] HU H,XIAO W J,YUAN J,et al.Preparations of TiO2film coated on foam nickel substrate by sol-gel processes and its photocatalytic activity for degradation of acetaldehyde[J].Journal of Environmental Sciences,2007,19(1):80-85.DOI:10.1016/S1001-0742(07)60013-8.
[10]刘燕辉,盛晓波,董寅生,等.纳米TiO2在泡沫镍上的负载技术研究[J].应用化工,2009,38(1):80-88.DOI:10.16581/j.cnki.issn1671-3206.2009.01.039.LIU Y H,SHENG X B,DONG Y S,et al.Study on the load of nano-TiO2 on nickel foam[J].Applied Chemical Industry,2009,38(1):80-88.DOI:10.16581/j.cnki.issn1671-3206.2009.01.039(Ch).
[11]张茂林,安太成,胡晓洪,等.泡沫镍负载纳米ZnOSnO2光催化降解三氯乙烯[J].环境科学学报,2005,25(2):259-263.DOI:10.13671/j.hjkxxb.2005.02.023.ZHANG M L,AN T C,HU X H,et al.Photocatalytic degradation of trichloroethylene in air on nanometer ZnO-SnO2 coupled oxides supported onto the porous nickel mesh[J].Acta Scientiae Circumstantiae,2005,25(2):259-263.DOI:10.13671/j.hjkxxb.2005.02.023(Ch).
[12]肖媛,王高鸿,刘永定.在不同营养条件下铜绿微囊藻对模拟微重力胁迫的响应[J].水生生物学报,2011,35(2):300-306.DOI:10.3724/SP.J.1035.2011.00300.XIAO Y,WANG G H,LIU Y D.Response of Microcystis aeruginosa to simulated microgravity stress under different nutritional conditions[J].Acta Hydrobiologica Sinica,2011,35(2):300-306.DOI:10.3724/SP.J.1035.2011.00300(Ch).
[13]赵远,谷娜,李恒,等.可见光下亚微米Cu2O微球光催化去除铜绿微囊藻[J].环境污染与防治,2016,38(4):45-50.DOI:10.15985/J.cnki.1001-3865.2016.01.009.ZHAO Y,GU N,LI H,et al.Photocatalytic removal of Microcystis aeruginosa by sub-micron Cu2O microspheres under visible light[J].Environmental Pollution Control,2016,38(4):45-50.DOI:10.15985/J.cnki.1001-3865.2016.01.009(Ch).
[14]WANG J,ZHAO F,CHEN B H,et al.Small water clusters stimulate microcystin biosynthesis in cyanobacterial Microcystis aeruginosa[J].Journal of Applied Phycology,2013,25(1):329-336.DOI:10.1007/s10811-012-9867-4.
[15]SONG J K,WANG X J,MA J X,et al.Removal of Microcystis aeruginosa and Microcystin-LR using a graphitic-C3N4/TiO2floating photocatalyst under visible light irradiation[J].Chemical Engineering Journal,2018,348:380-388.DOI:10.1016/j.cej.2018.04.182.
[16]邓祥元,成婕,周伟华,等.UV-B辐射对聚球藻7942生长及生理特性的影响[J].江苏农业科学,2014,42(5):281-283.DOI:10.15889/j.issn.1002-1302.2014.05.032.DENG X Y,CHENG J,ZHOU W H,et al.Effects of UV-B radiation on the growth and physiological characteristics of synechococcus 7492[J].Jiangsu Agricultural Sciences,2014,42(5):281-283.DOI:10.15889/j.issn.1002-1302.2014.05.032(Ch).
[17]CHEN D L,LIU M N,YIN L L,et al.Single-crystalline MoO3 nanoplates:Topochemical synthesis and enhanced ethanol-sensing performance[J].Journal of Materials Chemistry,2011,21(25):9332-9342.DOI:10.1039/c1jm11447f.
[18]徐志昌,张萍.MoO3纳米材料化学合成流程的研究[J].中国钼业,2010,34(1):6-20.DOI:10.13384/j.cnki.cmi.1006-2602.2010.01.002.XU Z C,ZHANG P.Study on chemical synthesis process for preparing nanomaterials of molybdenum trioxide[J].China Molybdenum Industry,2010,34(1):6-20.DOI:10.13384/j.cnki.cmi.1006-2602.2010.01.002(Ch).
[19]谢淑婷.基于咪哇类离子液体的液相法制备α-Fe2O3纳米材料[D].济南:山东大学,2015.XIE S T.Preparation ofα-Fe2O3 Nanostructures Using Imidozalium-Type Ionic Liquids-Moduated Solution Phase Methods[D].Jinan:Shandong University,2015(Ch).
[20]WILLIAM W,MARY W,STEVEN H,et al.Status of methods for assessing bacterial cell surface charge properties based on zeta potential measurements[J].Journal of Microbiological Methods,2001,43(3):153-164.DOI:10.1016/S0167-7012(00)00224-4.
[21]赵孟绪,韩博平.汤溪水库蓝藻水华发生的影响因子分析[J].生态学报,2005,25(7):1554-1567.DOI:10.3321/j.issn:1000-0933.2005.07.004.ZHAO M X,HAN B P.Analysis of factors affecting cyanobacteria bloom in a tropical reservoir(Tangxi Reservoir,China)[J].Acta Ecologica Sinica,2005,25(7):1554-1567.DOI:10.3321/j.issn:1000-0933.2005.07.004(Ch).
[22]中华人民共和国卫生部.GB/T 5750.6-2006生活饮用水标准检测方法金属指标[S].北京:中国标准出版社,2006.People’s Republic of China,Ministry of Health.GB/T 5750.6-2006 StandardExamination Methodsfor Drinking WaterMetal Parameters[S]. Beijing:Standards Press of China,2006(Ch).
[2] HYENSTRAND P,ROHRLACK T,BEATTIE K,et al.Laboratory studies of dissolved radiolabelled Microcystin-LR in lake water[J].Water Research,2003,37(14):3299-3306.DOI:10.1016/S0043-1354(03)00180-5.
[3] GU N,GAO J L,LI H,et al.Montmorillonite-supported with Cu2O nanoparticles for damage and removal of Microcystis aeruginosa under visible light[J].Applied Clay Science,2016,132-133:79-89.DOI:10.1016/j.clay.2016.05.017.
[4] YU X J,ZHOU J Y,WANG Z P,et al.Medium optimisation for improved growth-rate inhibition of Microcystis aeruginosa exposed to AgBiO3 using response-surface methodology[J].Advanced Materials Research,2011,255-260:2940-2948.DOI:10.4028/www.scientific.net/AMR.255-260.2940.
[5] SONG J K,WANG X J,MA J X,et al.Visible-lightdriven in situ inactivation of Microcystis aeruginosa with the use of floating g-C3N4 heterojunction photocatalyst:Performance,mechanisms and implications[J].Applied Catalysis B Environmental,2018,226(15):83-92.DOI:10.1016/j.apcatb.2017.12.034.
[6] ZHANG G Y,FENG Y,XU Y Y,et al.Controlled synthesis of mesoporousα-Fe2O3nanorods and visible light photocatalytic property[J].Materials Research Bulletin,2012,47(3):625-630.DOI:10.1016/j.materresbull.2011.12.032.
[7] WANG Y M,YU T,CHEN X Y,et al.Enhancement of photoelectric conversion properties of SrTiO3/α-Fe2O3 heterojunction photoanode[J].Journal of Physics D Applied Physics,2007,40(13):3925-3930.DOI:10.1088/0022-3727/40/13/003.
[8]甄延忠,王杰,王丹军,等.一维Fe2O3/α-MoO3异质结的制备及其可见光光催化性能[J].人工晶体学报,2017,46(1):55-62.DOI:10.16553/j.cnki.issn1000-985x.2017.01.010.ZHEN Y Z,WANG J,WANG D J,et al.Preparation and visible-light photocatalytic properties of one dimensional Fe2O3/α-MoO3heterostructures[J].Journal of Synthetic Crystals,2017,46(1):55-62.DOI:10.16553/j.cnki.issn1000-985x.2017.01.010(Ch).
[9] HU H,XIAO W J,YUAN J,et al.Preparations of TiO2film coated on foam nickel substrate by sol-gel processes and its photocatalytic activity for degradation of acetaldehyde[J].Journal of Environmental Sciences,2007,19(1):80-85.DOI:10.1016/S1001-0742(07)60013-8.
[10]刘燕辉,盛晓波,董寅生,等.纳米TiO2在泡沫镍上的负载技术研究[J].应用化工,2009,38(1):80-88.DOI:10.16581/j.cnki.issn1671-3206.2009.01.039.LIU Y H,SHENG X B,DONG Y S,et al.Study on the load of nano-TiO2 on nickel foam[J].Applied Chemical Industry,2009,38(1):80-88.DOI:10.16581/j.cnki.issn1671-3206.2009.01.039(Ch).
[11]张茂林,安太成,胡晓洪,等.泡沫镍负载纳米ZnOSnO2光催化降解三氯乙烯[J].环境科学学报,2005,25(2):259-263.DOI:10.13671/j.hjkxxb.2005.02.023.ZHANG M L,AN T C,HU X H,et al.Photocatalytic degradation of trichloroethylene in air on nanometer ZnO-SnO2 coupled oxides supported onto the porous nickel mesh[J].Acta Scientiae Circumstantiae,2005,25(2):259-263.DOI:10.13671/j.hjkxxb.2005.02.023(Ch).
[12]肖媛,王高鸿,刘永定.在不同营养条件下铜绿微囊藻对模拟微重力胁迫的响应[J].水生生物学报,2011,35(2):300-306.DOI:10.3724/SP.J.1035.2011.00300.XIAO Y,WANG G H,LIU Y D.Response of Microcystis aeruginosa to simulated microgravity stress under different nutritional conditions[J].Acta Hydrobiologica Sinica,2011,35(2):300-306.DOI:10.3724/SP.J.1035.2011.00300(Ch).
[13]赵远,谷娜,李恒,等.可见光下亚微米Cu2O微球光催化去除铜绿微囊藻[J].环境污染与防治,2016,38(4):45-50.DOI:10.15985/J.cnki.1001-3865.2016.01.009.ZHAO Y,GU N,LI H,et al.Photocatalytic removal of Microcystis aeruginosa by sub-micron Cu2O microspheres under visible light[J].Environmental Pollution Control,2016,38(4):45-50.DOI:10.15985/J.cnki.1001-3865.2016.01.009(Ch).
[14]WANG J,ZHAO F,CHEN B H,et al.Small water clusters stimulate microcystin biosynthesis in cyanobacterial Microcystis aeruginosa[J].Journal of Applied Phycology,2013,25(1):329-336.DOI:10.1007/s10811-012-9867-4.
[15]SONG J K,WANG X J,MA J X,et al.Removal of Microcystis aeruginosa and Microcystin-LR using a graphitic-C3N4/TiO2floating photocatalyst under visible light irradiation[J].Chemical Engineering Journal,2018,348:380-388.DOI:10.1016/j.cej.2018.04.182.
[16]邓祥元,成婕,周伟华,等.UV-B辐射对聚球藻7942生长及生理特性的影响[J].江苏农业科学,2014,42(5):281-283.DOI:10.15889/j.issn.1002-1302.2014.05.032.DENG X Y,CHENG J,ZHOU W H,et al.Effects of UV-B radiation on the growth and physiological characteristics of synechococcus 7492[J].Jiangsu Agricultural Sciences,2014,42(5):281-283.DOI:10.15889/j.issn.1002-1302.2014.05.032(Ch).
[17]CHEN D L,LIU M N,YIN L L,et al.Single-crystalline MoO3 nanoplates:Topochemical synthesis and enhanced ethanol-sensing performance[J].Journal of Materials Chemistry,2011,21(25):9332-9342.DOI:10.1039/c1jm11447f.
[18]徐志昌,张萍.MoO3纳米材料化学合成流程的研究[J].中国钼业,2010,34(1):6-20.DOI:10.13384/j.cnki.cmi.1006-2602.2010.01.002.XU Z C,ZHANG P.Study on chemical synthesis process for preparing nanomaterials of molybdenum trioxide[J].China Molybdenum Industry,2010,34(1):6-20.DOI:10.13384/j.cnki.cmi.1006-2602.2010.01.002(Ch).
[19]谢淑婷.基于咪哇类离子液体的液相法制备α-Fe2O3纳米材料[D].济南:山东大学,2015.XIE S T.Preparation ofα-Fe2O3 Nanostructures Using Imidozalium-Type Ionic Liquids-Moduated Solution Phase Methods[D].Jinan:Shandong University,2015(Ch).
[20]WILLIAM W,MARY W,STEVEN H,et al.Status of methods for assessing bacterial cell surface charge properties based on zeta potential measurements[J].Journal of Microbiological Methods,2001,43(3):153-164.DOI:10.1016/S0167-7012(00)00224-4.
[21]赵孟绪,韩博平.汤溪水库蓝藻水华发生的影响因子分析[J].生态学报,2005,25(7):1554-1567.DOI:10.3321/j.issn:1000-0933.2005.07.004.ZHAO M X,HAN B P.Analysis of factors affecting cyanobacteria bloom in a tropical reservoir(Tangxi Reservoir,China)[J].Acta Ecologica Sinica,2005,25(7):1554-1567.DOI:10.3321/j.issn:1000-0933.2005.07.004(Ch).
[22]中华人民共和国卫生部.GB/T 5750.6-2006生活饮用水标准检测方法金属指标[S].北京:中国标准出版社,2006.People’s Republic of China,Ministry of Health.GB/T 5750.6-2006 StandardExamination Methodsfor Drinking WaterMetal Parameters[S]. Beijing:Standards Press of China,2006(Ch).