纳米级Fe_3O_4-Pd/Fe复合材料催化脱氯2,4-D研究
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摘要
采用共沉淀法制备纳米级Fe_3O_4,将其包覆在纳米Pd/Fe颗粒表面制成纳米级Fe_3O_4-Pd/Fe复合材料,并用于2,4-二氯苯氧乙酸(2,4-D)的催化脱氯.同时,采用透射电镜(TEM)、扫描电镜(SEM)等方法对复合材料的结构进行分析,并考察了初始pH、钯化率、反应温度、纳米Fe_3O_4投加量等实验参数对n Fe_3O_4-Pd/Fe复合材料催化脱氯2,4-D的影响.结果发现,纳米Fe_3O_4粒径小于Pd/Fe纳米颗粒,具有一定的磁性,包覆于纳米Pd/Fe表面,提高了纳米材料的稳定性及分散性,并有利于复合材料的回收和循环利用.此外,纳米Fe_3O_4具有一定的导电性,可作为良好的电子通道为纳米Pd/Fe颗粒传递电子,促进反应的进行,增强2,4-D的去除效果.实验结果表明,较高的钯化率、反应温度、Fe_3O_4∶Fe质量比及中性pH条件均有利于反应的进行.当纳米Fe投加量为1.0 g·L-1,m(Fe_3O_4)∶m(Fe)为1∶1,初始pH为7.0,钯化率为0.15%,反应温度为25.0℃时,反应90 min后,40.0 mg·L-1的2,4-D的去除率达到100%,苯氧乙酸(PA)的生成率达99.8%.
In the present study,Fe_3O_4 nanoparticles were initially prepared and loaded on nano Pd/Fe surface to form n Fe_3O_4-Pd/Fe,and the synthesized composite was used for catalytic dechlorination of 2,4-dichlorophenoxyacetic acid( 2,4-D) in aqueous solution. This composites were systematically characterized by using Transmission electron microscope( TEM),Scanning electron microscopy( SEM). Operating parameters including initial pH,palladium loading rate,temperature and dosage of Fe_3O_4 nanoparticles on 2,4-D reduction were investigated. Results demonstrate that the magnetic Fe_3O_4 coated on the surface of nanoscale Pd/Fe improved the stability and dispersion capability of nanomaterials. In addition,Fe_3O_4 served as a good channel for electron transfer from nano Pd/Fe particles and enhanced the removal of 2,4-D. Under the optimized reaction conditions( n Fe_3O_41.0 g·L-1,n Fe 1.0 g·L-1,T = 25. 0 ℃,Pd/Fe = 0. 15%,n = 200 r·min-1,pH = 7.0),40.0 mg·L-12,4-D was almost completely converted into phenoxyacetic acid( PA) just in 90 min. The findings from this study suggestes that the dechlorination of 2,4-D by nanoscale Pd/Fe was significantly enhanced with Fe_3O_4 nanoparticles and can be a promising solution for catalytic dechlorination of 2,4-D.
In the present study,Fe_3O_4 nanoparticles were initially prepared and loaded on nano Pd/Fe surface to form n Fe_3O_4-Pd/Fe,and the synthesized composite was used for catalytic dechlorination of 2,4-dichlorophenoxyacetic acid( 2,4-D) in aqueous solution. This composites were systematically characterized by using Transmission electron microscope( TEM),Scanning electron microscopy( SEM). Operating parameters including initial pH,palladium loading rate,temperature and dosage of Fe_3O_4 nanoparticles on 2,4-D reduction were investigated. Results demonstrate that the magnetic Fe_3O_4 coated on the surface of nanoscale Pd/Fe improved the stability and dispersion capability of nanomaterials. In addition,Fe_3O_4 served as a good channel for electron transfer from nano Pd/Fe particles and enhanced the removal of 2,4-D. Under the optimized reaction conditions( n Fe_3O_41.0 g·L-1,n Fe 1.0 g·L-1,T = 25. 0 ℃,Pd/Fe = 0. 15%,n = 200 r·min-1,pH = 7.0),40.0 mg·L-12,4-D was almost completely converted into phenoxyacetic acid( PA) just in 90 min. The findings from this study suggestes that the dechlorination of 2,4-D by nanoscale Pd/Fe was significantly enhanced with Fe_3O_4 nanoparticles and can be a promising solution for catalytic dechlorination of 2,4-D.
引文
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Bae S,Lee W.2010.Inhibition of n ZVI reactivity by magnetite during the reductive degradation of 1,1,1-TAC in n ZVI/magnetite suspension[J].Applied Catalysis B:Environmental,96(1/2):10-17
Chaparadza A,Hossenlopp J M.2011.Removal of 2,4-dichlorophenoxyacetic acid by calcined Zn-Al-Zr layered double hydroxide[J].Journal of Colloid&Interface Science,363(1):92-97
Choi H,Al-abed S R,Agarwa S,et al.2008.Synthesis of reactive nano-Fe/Pd bimetallic system-impregnated activated carbon for the simultaneous adsorption and dechlorination of PCBs[J].Chemistry of Materials,20(11):3649-3655
Clark C J,Rao P S C,Annable M D.2003.Degradation of perchloroethylene in cosolvent solutions by zero-valent iron[J].Journal of Hazardous Materials,96(1/3):65-78
Guo X,Yang Z,Liu H,et al.2015.Common oxidants activate the reactivity of zero-valent iron(ZVI)and hence remarkably enhance nitrate reduction from water[J].Separation&Purification Technology,146:227-234
Guan X,Sun Y,Qin H,et al.2015.The limitations of applying zero-valent iron technology in contaminants sequestration and the corresponding countermeasures:The development in zero-valent iron technology in the last two decades(1994-2014)[J].Water Research,75:224-248
Graham L J,Jovanovic G.1999.Dechlorination of p-chlorophenol on a Pd/Fe catalyst in a magnetically stabilized fluidized bed;Implications for sludge and liquid remediation[J].Chemical Engineering Science,54(15/16):3085-3093
Harendra S,Vipulanandan C.2008.Degradation of high concentrations of PCE solubilized in SDS and biosurfactant with Fe/Ni bi-metallic particles[J].Colloids&Surfaces A Physicochemical&Engineering Aspects,322(1/3):6-13
Hui M,Huang Y,Shen M,et al.2012.Enhanced dechlorination of trichloroethylene using electrospun polymer nanofibrous mats immobilized with iron/palladium bimetallic nanoparticles[J].Journal of Hazardous Materials,211-212(2):349-356
黄园英,刘菲,汤鸣臬,等.2007.纳米镍/铁和铜/铁双金属对四氯乙烯脱氯研究[J].环境科学学报,27(1):80-85
Kustov L M,Finashina E D,Shuvalova E V,et al.2011.Pd-Fe nanoparticles stabilized by chitosan derivatives for perchloroethene dechlorination[J].Environmental International,37(6):1044-1052
Kustov L M,Al-Abed S R,Virkutyte J,et al.2014.Novel Fe-Pd/Si O2catalytic materials for degradation of chlorinated organic compounds in water[J].Pure&Applied Chemistry,86(7):1141-1158
Kakavandi B,Kalantary R R,Farzadkia M,et al.2014.Enhanced chromium(VI)removal using activated carbon modified by zero valent iron and silver bimetallic nanoparticles[J].Journal of Environmental Health Science and Engineering,12(1):115-124
Leupin O X,Hug S J.2005.Oxidation and removal of arsenic(III)from aerated groundwater by filtration through sand and zero-valent iron[J].Water Research,39(9):1729-1740
Lv X S,Xu J,Jiang G M,et al.2012.Highly active nanoscale zero-valent iron(n ZVI)-Fe3O4nanocomposites for the removal of chromium(Ⅵ)from aqueous solutions[J].Journal of Colloid Interface Science,369(1):460-469
Liu Y H,Yang F L,Chen G H,et al.2001.Catalytic dechlorination of chlorophenols in water by palladium/iron[J].Water Research,35(8):1887-1890
Nam S,Tratnyek P G.2000.Reduction of azo dyes with zero-valent iron[J].Water Research,34(6):1837-1845
Nejati K,Davary S,Saati M.2013.Study of 2,4-dichlorophenoxyacetic acid(2,4-D)removal by Cu-Fe-layered double hydroxide from aqueous solution[J].Applied Surface Science,280(9):67-73
O'Carroll D,Sleep B,Krol M,et al.2013.Nanoscale zero valent iron and bimetallic particles for contaminated site remediation[J].Advances in Water Resources,51(1):104-122
Parshetti G K,Doong R.2009.Dechlorination of trichloroethylene by Ni/Fe nanoparticles immobilized in PEG/PVDF and PEG/nylon 66membranes[J].Water Research,43(12):3086-3094
Parsons J G,Hernandez J,Gonzalez C M,et al.2014.Sorption of Cr(III)and Cr(VI)to high and low pressure synthetic nano-magnetite(Fe3O4)particles[J].Chemical Engineering Journal,254(7):171-180
Pascual A,Ares J R,Ferrer I J,et al.2004.Electrical resistance evolution of thin films during their sulphuration process[J].Applied Surface Science,234(1/4):355-361
Song Y.2014.Insight into the mode of action of 2,4-dichlorophenoxyacetic acid(2,4-D)as an herbicide[J].Journal of Integrative Plan Biology,56(2):106-113
Su J,Lin S,Chen Z L,et al.2011.Dechlorination of p-chlorophenol from aqueous solution using bentonite supported Fe/Pd nanoparticles:synthesis,characterization and kinetics[J].Desalination,280(1/3):167-173
Shin M,Choi H,Kim D,et al.2008.Effect of surfactant on reductive dechlorination of trichloroethylene by zero-valent iron[J].Desalination,223(1/3):299-307
Shih Y H,Hsu C Y,Su Y F.2011.Reduction of hexachlorobenzene by nanoscale zero-valent iron:Kinetics,p H effect,and degradation mechanism[J].Separation and Purification Technology,76(3):268-274
Sun Y P,Li X Q,Cao J,et al.2006.Characterization of zero-valent iron nanoparticles[J].Advances in Colloid&Interface Science,120(1/3):47-56
Wang S,Ge L,Li L,et al.2013.Molecularly imprinted polymer grafted paper-based multi-disk micro-disk plate for chemiluminescence detection of pesticide[J].Biosensors&Bioelectronics,50C(23):262-268
Wang C B,Zhang W X.1997.Synthesizing Nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs[J].Environmental Science Technology,31(7):2154-2156
Wu L,Ritchie S M C.2008.Enhanced dechlorination of trichloroethylene by membrane-supported Pd-coated iron nanoparticles[J].Environmental Progress,27(2):218-224
Xu L J,Wang J L.2012.Fenton-like degradation of 2,4-dichlorophenol using Fe3O4magnetic nanoparticles[J].Applied Catalysis B:Environmental,123-124(30):117-126
徐新华,金剑,卫建军,等.2004.纳米Pd/Fe双金属对2,4-二氯酚的脱氯机理及动力学[J].环境科学学报,24(4):561-567
Yang B,Yu G,Liu X.2007.Electrochemical hydrodechlorination of 4-chlorobiphenyl in aqueous solution with the optimization of palladium-loaded cathode materials[J].Electrochimica Acta,52(3):1075-1081
Zhou H Y,Wang S C,Sheng G D.2010.Catalytic dechlorination and detoxification of 1-(2-chlorophenyl)ethanol by Pd/Fe[J].Journal of Zhejiang University-Science A,11(5):356-362
Zhang Z,Shen Q,Cissoko N,et al.2010.Catalyticdechlorination of 2,4-dichlorophenol by Pd/Fe bimetallic nanoparticles in the presence of humic acid[J].Journal of Hazardous Materials,182(1/3):252-258
Bae S,Lee W.2010.Inhibition of n ZVI reactivity by magnetite during the reductive degradation of 1,1,1-TAC in n ZVI/magnetite suspension[J].Applied Catalysis B:Environmental,96(1/2):10-17
Chaparadza A,Hossenlopp J M.2011.Removal of 2,4-dichlorophenoxyacetic acid by calcined Zn-Al-Zr layered double hydroxide[J].Journal of Colloid&Interface Science,363(1):92-97
Choi H,Al-abed S R,Agarwa S,et al.2008.Synthesis of reactive nano-Fe/Pd bimetallic system-impregnated activated carbon for the simultaneous adsorption and dechlorination of PCBs[J].Chemistry of Materials,20(11):3649-3655
Clark C J,Rao P S C,Annable M D.2003.Degradation of perchloroethylene in cosolvent solutions by zero-valent iron[J].Journal of Hazardous Materials,96(1/3):65-78
Guo X,Yang Z,Liu H,et al.2015.Common oxidants activate the reactivity of zero-valent iron(ZVI)and hence remarkably enhance nitrate reduction from water[J].Separation&Purification Technology,146:227-234
Guan X,Sun Y,Qin H,et al.2015.The limitations of applying zero-valent iron technology in contaminants sequestration and the corresponding countermeasures:The development in zero-valent iron technology in the last two decades(1994-2014)[J].Water Research,75:224-248
Graham L J,Jovanovic G.1999.Dechlorination of p-chlorophenol on a Pd/Fe catalyst in a magnetically stabilized fluidized bed;Implications for sludge and liquid remediation[J].Chemical Engineering Science,54(15/16):3085-3093
Harendra S,Vipulanandan C.2008.Degradation of high concentrations of PCE solubilized in SDS and biosurfactant with Fe/Ni bi-metallic particles[J].Colloids&Surfaces A Physicochemical&Engineering Aspects,322(1/3):6-13
Hui M,Huang Y,Shen M,et al.2012.Enhanced dechlorination of trichloroethylene using electrospun polymer nanofibrous mats immobilized with iron/palladium bimetallic nanoparticles[J].Journal of Hazardous Materials,211-212(2):349-356
黄园英,刘菲,汤鸣臬,等.2007.纳米镍/铁和铜/铁双金属对四氯乙烯脱氯研究[J].环境科学学报,27(1):80-85
Kustov L M,Finashina E D,Shuvalova E V,et al.2011.Pd-Fe nanoparticles stabilized by chitosan derivatives for perchloroethene dechlorination[J].Environmental International,37(6):1044-1052
Kustov L M,Al-Abed S R,Virkutyte J,et al.2014.Novel Fe-Pd/Si O2catalytic materials for degradation of chlorinated organic compounds in water[J].Pure&Applied Chemistry,86(7):1141-1158
Kakavandi B,Kalantary R R,Farzadkia M,et al.2014.Enhanced chromium(VI)removal using activated carbon modified by zero valent iron and silver bimetallic nanoparticles[J].Journal of Environmental Health Science and Engineering,12(1):115-124
Leupin O X,Hug S J.2005.Oxidation and removal of arsenic(III)from aerated groundwater by filtration through sand and zero-valent iron[J].Water Research,39(9):1729-1740
Lv X S,Xu J,Jiang G M,et al.2012.Highly active nanoscale zero-valent iron(n ZVI)-Fe3O4nanocomposites for the removal of chromium(Ⅵ)from aqueous solutions[J].Journal of Colloid Interface Science,369(1):460-469
Liu Y H,Yang F L,Chen G H,et al.2001.Catalytic dechlorination of chlorophenols in water by palladium/iron[J].Water Research,35(8):1887-1890
Nam S,Tratnyek P G.2000.Reduction of azo dyes with zero-valent iron[J].Water Research,34(6):1837-1845
Nejati K,Davary S,Saati M.2013.Study of 2,4-dichlorophenoxyacetic acid(2,4-D)removal by Cu-Fe-layered double hydroxide from aqueous solution[J].Applied Surface Science,280(9):67-73
O'Carroll D,Sleep B,Krol M,et al.2013.Nanoscale zero valent iron and bimetallic particles for contaminated site remediation[J].Advances in Water Resources,51(1):104-122
Parshetti G K,Doong R.2009.Dechlorination of trichloroethylene by Ni/Fe nanoparticles immobilized in PEG/PVDF and PEG/nylon 66membranes[J].Water Research,43(12):3086-3094
Parsons J G,Hernandez J,Gonzalez C M,et al.2014.Sorption of Cr(III)and Cr(VI)to high and low pressure synthetic nano-magnetite(Fe3O4)particles[J].Chemical Engineering Journal,254(7):171-180
Pascual A,Ares J R,Ferrer I J,et al.2004.Electrical resistance evolution of thin films during their sulphuration process[J].Applied Surface Science,234(1/4):355-361
Song Y.2014.Insight into the mode of action of 2,4-dichlorophenoxyacetic acid(2,4-D)as an herbicide[J].Journal of Integrative Plan Biology,56(2):106-113
Su J,Lin S,Chen Z L,et al.2011.Dechlorination of p-chlorophenol from aqueous solution using bentonite supported Fe/Pd nanoparticles:synthesis,characterization and kinetics[J].Desalination,280(1/3):167-173
Shin M,Choi H,Kim D,et al.2008.Effect of surfactant on reductive dechlorination of trichloroethylene by zero-valent iron[J].Desalination,223(1/3):299-307
Shih Y H,Hsu C Y,Su Y F.2011.Reduction of hexachlorobenzene by nanoscale zero-valent iron:Kinetics,p H effect,and degradation mechanism[J].Separation and Purification Technology,76(3):268-274
Sun Y P,Li X Q,Cao J,et al.2006.Characterization of zero-valent iron nanoparticles[J].Advances in Colloid&Interface Science,120(1/3):47-56
Wang S,Ge L,Li L,et al.2013.Molecularly imprinted polymer grafted paper-based multi-disk micro-disk plate for chemiluminescence detection of pesticide[J].Biosensors&Bioelectronics,50C(23):262-268
Wang C B,Zhang W X.1997.Synthesizing Nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs[J].Environmental Science Technology,31(7):2154-2156
Wu L,Ritchie S M C.2008.Enhanced dechlorination of trichloroethylene by membrane-supported Pd-coated iron nanoparticles[J].Environmental Progress,27(2):218-224
Xu L J,Wang J L.2012.Fenton-like degradation of 2,4-dichlorophenol using Fe3O4magnetic nanoparticles[J].Applied Catalysis B:Environmental,123-124(30):117-126
徐新华,金剑,卫建军,等.2004.纳米Pd/Fe双金属对2,4-二氯酚的脱氯机理及动力学[J].环境科学学报,24(4):561-567
Yang B,Yu G,Liu X.2007.Electrochemical hydrodechlorination of 4-chlorobiphenyl in aqueous solution with the optimization of palladium-loaded cathode materials[J].Electrochimica Acta,52(3):1075-1081
Zhou H Y,Wang S C,Sheng G D.2010.Catalytic dechlorination and detoxification of 1-(2-chlorophenyl)ethanol by Pd/Fe[J].Journal of Zhejiang University-Science A,11(5):356-362
Zhang Z,Shen Q,Cissoko N,et al.2010.Catalyticdechlorination of 2,4-dichlorophenol by Pd/Fe bimetallic nanoparticles in the presence of humic acid[J].Journal of Hazardous Materials,182(1/3):252-258