纳米钯/铁双金属体系对氯乙酸还原脱氯研究
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摘要
零价铁作为一种廉价、简单有效的脱氯还原剂,其在处理氯代有机物方面的作用已经得到了普遍肯定。为了提高铁催化还原的效率,人们采用纳米钯/铁双金属颗粒,膜载纳米钯/铁双金属颗粒对氯代有机物进行还原脱氯研究。
本文采用化学沉淀法制备了纳米钯/体双金属颗粒,采用交联浸涂法制备了载有纳米钯/铁双金属颗粒的催化还原膜,并对纳米钯/铁双金属颗粒和载有纳米钯/铁双金属颗粒的催化还原膜进行了系统研究。
通过透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X-射线衍射光谱(XRD)、X射线荧光光谱(XRF)、能谱分析(EDS)、BET-N2比表面积等分析检测手段,表征了纳米级Pd/Fe双金属颗粒的形状、大小、晶体结构、钯化率及其比表面积。本研究制备的纳米钯/铁双金属颗粒中Fe主要以α-Fe0形式存在。纳米钯/铁双金属颗粒的直径约为30-50nm,比表面积约51m2/g。
采用纳米钯/铁双金属颗粒对一氯乙酸进行还原脱氯研究。比较不同还原剂对一氯乙酸还原脱氯效果,考察了纳米钯/铁双金属颗粒投加量、纳米钯/铁双金属颗粒钯化率对一氯乙酸还原脱氯效果影响。结果表明纳米钯/铁双金属颗粒对一氯乙酸还原脱氯的脱氯率是还原铁粉和纳米铁粉对一氯乙酸还原脱氯的脱氯率的7.9倍和1.7倍。在实验条件下纳米钯/铁双金属颗粒投加量为10g/L,钯化率为0.083%时,纳米钯/铁双金属颗粒对一氯乙酸还原脱氯效果最好。
采用纳米钯/铁双金属颗粒对三氯乙酸进行还原脱氯研究,发现在反应1min内90%以上的三氯乙酸被还原脱氯为二氯乙酸,二氯乙酸在反应30min后基本全部被还原脱氯,产物为一氯乙酸,一氯乙酸随着反应时间的进行浓度先升高后下降。
采用等离子发射光谱和扫描电子显微镜对催化还原膜的钯化率和膜表面形貌进行了分析。发现实验制备的催化还原膜上纳米钯/铁双金属颗粒实测钯化率低于理论钯化率。HCPF催化还原膜上纳米钯/铁双金属颗粒分散效果效果好于HPF催化还原膜、CPF催化还原膜、PF催化还原膜。
采用四种工艺制备的催化还原膜对三氯乙酸进行还原脱氯研究。实验结果表明HCPF催化还原膜对三氯乙酸还原脱氯的修正反应速率常数是HPF催化还原膜、CPF催化还原膜、PF催化还原膜的2.1、4.2、7.8倍。
采用HCPF催化还原膜对三氯乙酸进行还原脱氯研究。考察了钯/铁双金属体系钯化率、催化还原膜投加量、催化还原膜稳定性、溶液水含量和溶液初始浓度对HCPF催化还原膜对三氯乙酸还原脱氯效果的影响。实验结果表明钯化率为0.534%,催化还原膜上纳米钯/铁双金属颗粒投加量多于5.08mg时,三氯乙酸的还原脱氯效果最好。催化还原膜稳定性实验结果表明本研究制备的HCPF催化还原膜可以连续使用四次而不影响三氯乙酸去除效果。水对三氯乙酸的还原脱氯起重要作用,在没有水存在的溶液中,三氯乙酸与载有纳米钯/铁双金属颗粒的催化还原膜不反应。随着三氯乙酸初始浓度的增加,催化还原膜对三氯乙酸的还原脱氯效果下降。
Iron plays an important role in reducing chlorinated organics for its efficiency and convenience. Nanoscale Pd/Fe bimetallic particles and membrane stabilized nanoscale Pd/Fe bimetallic particles were used to enhance dechlorination efficiency of iron.
Nanoscale Pd/Fe bimetallic particles were prepared by chemical deposition method. Membrane stabilized Pd/Fe bimetallic particles(hybrid membrane) were prepared by dip-coating method. Systematic work on nanoscale Pd/Fe bimetallic particles and membrane stabilized Pd/Fe bimetallic particles were conducted in this study.
Particle shape, size, crystal structure, Pd to Fe ratio(PFR) and specific surface area of nanoscale Pd/Fe bimetallic particles were studied by transmission electronic microscopy(TEM), scanning electron microscope(SEM), X-ray diffraction(XRD), X-ray fluorescence(XRF), enengy distribution spectra(EDS) and Brunauer-Emmett-Teller-nitrogen(BET) method. Iron element in nanoscale Pd/Fe bimetallic particles prepared in this study existed mainly asα-Fe0. The diameter and specific surface area of nanoscale Pd/Fe bimetallic particles were 30-50 nm and 51m2/g, respectively.
Nanoscale Pd/Fe bimetallic particles were used to dechlorinate monochloroacetic acid(MCAA). Dechlorination of MCAA with different reducts was studied. Effect of dose and PFR of nanoscale Pd/Fe bimetallic particles on dechlorination of MCAA was detected. Data showed that dechlorination efficiency(DE) of MCAA with nanoscale Pd/Fe bimetallic particles were 6.9 times and 0.7 times larger than that with reductive Fe and nanoscale Fe, respectively. When the amount of nanoscale Pd/Fe bimetallic particles were 10 g/L and PFR was 0.083%, DE of MCAA was the best.
Nanoscale Pd/Fe bimetallic particles were used to dechlorinate trichloroacetic acid(TCAA). More than 90% of TCAA were dechlorinated to dichloroacetic acid(DCAA) during the first 1 min of reaction. DCAA were dechlorinated completely to MCAA after 30 min and the concentration of MCAA in solution appeared a decrease trend after the increase.
Surface morphology and PFR of hybrid membrane were studied by inductively coupled plasma atomic emission spectrometer(ICP-AES) and SEM. It was found that metrical PFR of hybrid membrane was lower than theoretical PFR. Nanoscale Pd/Fe bimetallic particles stabilized in HCPF hybrid membrane congregated less than that in HPF, CPF and PF hybrid membranes.
Four kinds of hybrid membranes were used to dechlorinate TCAA. It was found that modified reaction rate constant of HCPF hybrid membrane was 2.1, 4.2 and 7.8 times as large as that of HPF hybrid membrane, CPF hybrid membrane and PF hybrid membrane, respectively.
HCPF hybrid membrane was used to dechlorinate TCAA. Effect of PFR of nanoscale Pd/Fe bimetallic particles stabilized in the hybrid membrane, dose of hybrid membrane, stability of hybrid membrane, H2O amount in solution and initial TCAA concentration on dechlorination of TCAA were detected. Data showed that dechlorination efficiency of TCAA could be the best when PFR was 0.534% and dose of nanoscale bimetallic particles stabilized in hybrid membrane was more than 5.08 mg. HCPF hybrid membrane could dechlorinate TCAA with the same dechlorination efficiency during the fist 4 repetition times. H2O plays an important role in dechlorination, and dechlorination of TCAA did not occur without H2O. Dechlorination effect of TCAA decreased as the initial concentration increased.
本文采用化学沉淀法制备了纳米钯/体双金属颗粒,采用交联浸涂法制备了载有纳米钯/铁双金属颗粒的催化还原膜,并对纳米钯/铁双金属颗粒和载有纳米钯/铁双金属颗粒的催化还原膜进行了系统研究。
通过透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X-射线衍射光谱(XRD)、X射线荧光光谱(XRF)、能谱分析(EDS)、BET-N2比表面积等分析检测手段,表征了纳米级Pd/Fe双金属颗粒的形状、大小、晶体结构、钯化率及其比表面积。本研究制备的纳米钯/铁双金属颗粒中Fe主要以α-Fe0形式存在。纳米钯/铁双金属颗粒的直径约为30-50nm,比表面积约51m2/g。
采用纳米钯/铁双金属颗粒对一氯乙酸进行还原脱氯研究。比较不同还原剂对一氯乙酸还原脱氯效果,考察了纳米钯/铁双金属颗粒投加量、纳米钯/铁双金属颗粒钯化率对一氯乙酸还原脱氯效果影响。结果表明纳米钯/铁双金属颗粒对一氯乙酸还原脱氯的脱氯率是还原铁粉和纳米铁粉对一氯乙酸还原脱氯的脱氯率的7.9倍和1.7倍。在实验条件下纳米钯/铁双金属颗粒投加量为10g/L,钯化率为0.083%时,纳米钯/铁双金属颗粒对一氯乙酸还原脱氯效果最好。
采用纳米钯/铁双金属颗粒对三氯乙酸进行还原脱氯研究,发现在反应1min内90%以上的三氯乙酸被还原脱氯为二氯乙酸,二氯乙酸在反应30min后基本全部被还原脱氯,产物为一氯乙酸,一氯乙酸随着反应时间的进行浓度先升高后下降。
采用等离子发射光谱和扫描电子显微镜对催化还原膜的钯化率和膜表面形貌进行了分析。发现实验制备的催化还原膜上纳米钯/铁双金属颗粒实测钯化率低于理论钯化率。HCPF催化还原膜上纳米钯/铁双金属颗粒分散效果效果好于HPF催化还原膜、CPF催化还原膜、PF催化还原膜。
采用四种工艺制备的催化还原膜对三氯乙酸进行还原脱氯研究。实验结果表明HCPF催化还原膜对三氯乙酸还原脱氯的修正反应速率常数是HPF催化还原膜、CPF催化还原膜、PF催化还原膜的2.1、4.2、7.8倍。
采用HCPF催化还原膜对三氯乙酸进行还原脱氯研究。考察了钯/铁双金属体系钯化率、催化还原膜投加量、催化还原膜稳定性、溶液水含量和溶液初始浓度对HCPF催化还原膜对三氯乙酸还原脱氯效果的影响。实验结果表明钯化率为0.534%,催化还原膜上纳米钯/铁双金属颗粒投加量多于5.08mg时,三氯乙酸的还原脱氯效果最好。催化还原膜稳定性实验结果表明本研究制备的HCPF催化还原膜可以连续使用四次而不影响三氯乙酸去除效果。水对三氯乙酸的还原脱氯起重要作用,在没有水存在的溶液中,三氯乙酸与载有纳米钯/铁双金属颗粒的催化还原膜不反应。随着三氯乙酸初始浓度的增加,催化还原膜对三氯乙酸的还原脱氯效果下降。
Iron plays an important role in reducing chlorinated organics for its efficiency and convenience. Nanoscale Pd/Fe bimetallic particles and membrane stabilized nanoscale Pd/Fe bimetallic particles were used to enhance dechlorination efficiency of iron.
Nanoscale Pd/Fe bimetallic particles were prepared by chemical deposition method. Membrane stabilized Pd/Fe bimetallic particles(hybrid membrane) were prepared by dip-coating method. Systematic work on nanoscale Pd/Fe bimetallic particles and membrane stabilized Pd/Fe bimetallic particles were conducted in this study.
Particle shape, size, crystal structure, Pd to Fe ratio(PFR) and specific surface area of nanoscale Pd/Fe bimetallic particles were studied by transmission electronic microscopy(TEM), scanning electron microscope(SEM), X-ray diffraction(XRD), X-ray fluorescence(XRF), enengy distribution spectra(EDS) and Brunauer-Emmett-Teller-nitrogen(BET) method. Iron element in nanoscale Pd/Fe bimetallic particles prepared in this study existed mainly asα-Fe0. The diameter and specific surface area of nanoscale Pd/Fe bimetallic particles were 30-50 nm and 51m2/g, respectively.
Nanoscale Pd/Fe bimetallic particles were used to dechlorinate monochloroacetic acid(MCAA). Dechlorination of MCAA with different reducts was studied. Effect of dose and PFR of nanoscale Pd/Fe bimetallic particles on dechlorination of MCAA was detected. Data showed that dechlorination efficiency(DE) of MCAA with nanoscale Pd/Fe bimetallic particles were 6.9 times and 0.7 times larger than that with reductive Fe and nanoscale Fe, respectively. When the amount of nanoscale Pd/Fe bimetallic particles were 10 g/L and PFR was 0.083%, DE of MCAA was the best.
Nanoscale Pd/Fe bimetallic particles were used to dechlorinate trichloroacetic acid(TCAA). More than 90% of TCAA were dechlorinated to dichloroacetic acid(DCAA) during the first 1 min of reaction. DCAA were dechlorinated completely to MCAA after 30 min and the concentration of MCAA in solution appeared a decrease trend after the increase.
Surface morphology and PFR of hybrid membrane were studied by inductively coupled plasma atomic emission spectrometer(ICP-AES) and SEM. It was found that metrical PFR of hybrid membrane was lower than theoretical PFR. Nanoscale Pd/Fe bimetallic particles stabilized in HCPF hybrid membrane congregated less than that in HPF, CPF and PF hybrid membranes.
Four kinds of hybrid membranes were used to dechlorinate TCAA. It was found that modified reaction rate constant of HCPF hybrid membrane was 2.1, 4.2 and 7.8 times as large as that of HPF hybrid membrane, CPF hybrid membrane and PF hybrid membrane, respectively.
HCPF hybrid membrane was used to dechlorinate TCAA. Effect of PFR of nanoscale Pd/Fe bimetallic particles stabilized in the hybrid membrane, dose of hybrid membrane, stability of hybrid membrane, H2O amount in solution and initial TCAA concentration on dechlorination of TCAA were detected. Data showed that dechlorination efficiency of TCAA could be the best when PFR was 0.534% and dose of nanoscale bimetallic particles stabilized in hybrid membrane was more than 5.08 mg. HCPF hybrid membrane could dechlorinate TCAA with the same dechlorination efficiency during the fist 4 repetition times. H2O plays an important role in dechlorination, and dechlorination of TCAA did not occur without H2O. Dechlorination effect of TCAA decreased as the initial concentration increased.
引文
1魏建荣,王振纲.水中消毒副产物研究进展.卫生研究. 2004,3(1): 115~118
2 R. J. Bull, F. C. Kopfler. Health Effects of Disinfectants and Disinfection By-products. AWWARF, Denver, 1991
3 K. Verschueren. Handbook of Environmental Data on Organic Chemicals. Van Nostrand Reinhold, 1983
4 B. L. Dvorak, D. F. Lawler. Selecting Among Physical/Chemical Processes for Removing Synthetic Oganics from Water. Water Environment Research. 1993,65(7): 827~838
5刘毅慧.水中氯代有机物催化还原脱氯的研究.大连理工大学博士学位. 1999: 13~19 20~21
6赵毅.多氯联苯催化转移氢化脱氯的研究.环境化学. 1994,13(4): 328~330
7 D. P. Sinatar, C. G. Schreier, C. Chi-Su, M. Reinhard. Treatment of 1,2-dibromo-3-chloropropane and Nitrate-contaminated Water with Zero-valentIron or Hydrogen/Palladium Catalysts. Water Research. 1996,30(10): 2315~2322
8 M. R. Kriegman-King, M. Reinhard. Transformation of Carbon Tetrachloride by Pyrite in Aqueous Solution. Environmental Science & Technol. 1994,28(4): 692~700
9 P. D. Hooker, K. J. Klaubunde. Destructive Adsorption of Carbon Tetrachloride on Iron(Ⅲ) Oxide. Environmental Science & Technology. 1994,28(7): 1243~1247
10 M. Erbs, H. C. B. Hansen, C. E. Olsen.Reductive Dechlorination of Carbon Tetrachloride Using Iron(Ⅱ)Iron(Ⅲ) Hydroxide Sulfate(green rust)．Environmental Science & Technology. 1999,33(2): 307~311
11 E. C. Butle, K. F. Hayes. Effects of Solution Composition and pH on the Reductive Dechlorination of Hexachloroethane by Iron Sulfide. Environmental Science & Technology. 1998,32(9): 1276~1284
12卫建军.纳米级Pd/Fe双金属对水中氯酚的催化脱氯研究.浙江大学博士学位. 2004: 8~10 14~18 20~21
13 R. M. Hozalski, L. Zhang, W. A. Arnold. Reduction of Haloacetic Acids by Fe：Implications for Treatment and Fate. Environmental Science & Technology.2001,35(11): 2258~2263
14周红艺等.含铁化合物对有机氯化物的脱氯处理技术研究.环境污染治理技术与设备. 2002,3(1): 52~56
15周红艺.钯/铁双金属体系对氯代芳烃的催化脱氯研究.浙江大学博士学位2003: 16
16全燮,杨凤林,薛大明,赵雅芝,冯文国,苍郁.钯-铁催化还原法对水中二氯乙烯的快速脱氯研究.人连理工大学学报. 1997,37(1): 46~48 107
17 R. Koch. Galvanic Action Water Purifier. U. S.–Pat. 1968. 3392102-A
18 E. K. Wilson. Zero-valent Metals Provide Possible Solution to Groundwater Problems. Chemical and Environment. 1995,73(21): 19~22
19 R. Muftikian, Q. Fernando, N. Korte. A Method for the Rapid Dechlorination of Low Molecular Weight Chlorinated Hydrocarbons in Water. Water Research. 1995, 29(10): 2434~2439
20全燮,刘会娟,杨凤林,薛大明,赵雅芝.二元金属体系对水中多氯有机物的催化还原脱氯特性.中国环境科学. 1998,18(4): 333~336
21 N. E. Korte, J. L. Zutman, R. M. Schlosser. Field Application of Palladized Iron for the Dechlorination of Trichloroethene. Waste Management. 2000,20(8): 687~694
22何小娟,汤鸣皋,沈照理,崔卫华,徐鹏. Ni/Fe双金属对PCE脱氯影响效果因素研究.地球科学-中国地质大学学报. 2003,28(3): 337~340
23何小娟,汤鸣皋,李旭东,徐鹏.镍/铁和铜/铁双金属降解四氯乙烯的研究.环境化学. 2003,22(4): 334~339
24 Y. H. Liu, F. L. Yang, P. L. Yue, G. H. Chen. Catalytic Dechlorination of Chlorophenols in Water by Palladium/Iron. Water Research. 2001,35(8): 1887~1890
25 L, J, Graham, G. Jovanovic. Dechlorination of P-chlorophenol on a Pd/FeCatalyst in A Magnetically Stabilized Fluidized Bed：Implications for Sludge and Liquid Remediation. Chemical Engineering Science. 1999,54(15-16): 3085~3093
26 Y. H. Kim, E. R. Carraway. Dechlorination of Pentachlorophenol by Zero Valent Iron and Modified Zero Valent Irons. Environmental Science & Technology.2000,34(10): 2014~2017
27 J. G. Doyle, T. Miles, E. Parker. Quantification of Total Polychlorinated Biphenylby Dechlorination to Biphenyl by Pd/Fe and Pd/Mg Bimetallic Particles. Microchemical Journal. 1998,60(3): 290~295
28 M. D. Engelmann, R. Hutcheson, K. Henschied, R. Neal, I. F. Cheng. Simultaneous Determination of Total Polychlorinated Biphenyl and Dichlorodiphenyltrichloroethane(DDT) by Dechlorination with Fe/Pd and Mg/Pd Bimetallic Particles and Flame Ionization Detection Gas Chromatography.Microchemical Journal. 2003,74(1): 19~25
29 W. X. Zhang, C. B. Wang, H. L. Lien. Treatment of Chlorinated Organic Contaminants with Nanoscale Bimetallic Particles. Catalysis Today. 1998,40(4): 387~395
30 H. L. Lien, W. X. Zhang. Transformation of Chlorinated Methanes by Nanoscale Iron Particles. Journal of Environmental Engineering. 1999,125(11): 1042~1047
31 H. L. Lien，W. X. Zhang. Nanoscale Iron Particles for Complete Reduction of Chlorinated Ethenes. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2001,191(1): 97~105.
32 D. W. Elliott, W. X. Zhang. Field Assessment of Nanoscale Bimetallic Particles for Groundwater Treatment. Environmental Science Technology. 2001,35(24): 4922~4926
33 S. Kidambi, M. L. Bruening, Multilayered Polyelectrolyte Films Containing Palladium Nanoparticles: Synthesis, Characterization, and application in Selective Hydrogenation. Chemistry of Materials. 2005,17(2): 301~307
34 L. Wu, M. Shamsuzzoha, S. M. C. Ritchie. Preparation of Cellulose Acetate Supported Zero-Valent Iron Nanoparticles for the Dechlorination of Trichloroethylene in Water. Journal of Nanoparticle Research. 2005,7(4-5): 469~476
35 J. K. Gotpagar, E. A. Grulke, T. Tsang, D. Bhattacharyya. Reductive Dehalogenation of Trichloroethylene Using Zero-Valent Iron. Environmental Progress. 1997,16(2): 137~143
36 F. Li, C. Vipulanandan, K. K. Mohanty. Microemulsion and Solution Approaches to Nanoparticle Iron Production for Degradation of Trichloroethylene. Colloids and Surfaces. A: Physicochemical and Engineering Aspects. 2003,223(1): 103~112
37 L. F. Wu, S. M. C. Ritchie. Removal of Trichloroethylene from Water byCellulose Acetate Supported Bimetallic Ni/Fe Nanoparticles. Chemosphere. 2006,63(2): 285~292
38 J. Xu, D. Bhattacharyya. Membrane-based Bimetallic Nanoparticles for Environmental Remediation: Synthesis and Reactive Properties. Environmental Progress. 2005,24(4): 358~366
39 T. C. Wang, M. F. Rubner, R. E. Cohen. Polyelectrolyte Multilayer Nanoreactors for Preparing Silver Nanoparticle Composites: Controlling Metal Concentration and Nanoparticle Size. Langmuir. 2002,18(8): 3370~3375.
40 J. Xu, D. Bhattacharyya. Fe/Pd Nanoparticle Immobilization in Microfiltration Membrane Pores: Synthesis, Characterization, and Application in the Dechlorination of Polychlorinated Biphenyls. Industrial Engineering Chemistry Research. 2007,46(8): 2348~2359.
41 L. J. Matheson, P. Q. Tratnyek. Reductive Dehalogenation of Chlorinated Methanes by Iron Metal. Environmental Science & Technology. 1994,28(12): 2045~2053
42 T. L. Johnson, M. M. Scherer, P. G. Tratnyek. Kinetics of Halogenated Organic Compound Degradation by Iron Metal. Environmental Science & Technology. 1996,30(8): 2634~2640.
43 R. Weerasooriya, B. Dharmasena. Pyrite-assisted Degradation of Trichloroethene. Chemosphere. 2001,42(4): 389~396
44 J. Xu, A. Dozier, D. Bhattacharyya. Synthesis of Nanoscale Bimetallic Particlesin Polyelectrolyte Membrane Matrix for Reductive Transformation of Halogenated Organic Compounds. Journal of Nanoparticle Research. 2005,7(4-5): 449~467
45周洁.聚偏氟乙烯膜的亲水改性及处理低浓度含油废水的研究.南京理工大学硕士学位论文. 2005: 10~19
46黎雁,吕晓龙.聚偏氟乙烯多孔膜的改性研究进展.天津工业大学学报. 2001,20(5): 74~78
47吴万国,丁音琴,黄清明.纳米材料晶粒鉴定方法的研究.福州大学学报(自然科学版). 2003,31(1):49～51
48周红艺,徐新华,汪大翚.钯/铁双金属对水中氯苯的催化脱氯研究.浙江大学学报(工学版) . 2003,37(3): 345~349
49 L. Zhang, W. A. Arnold, R. M. Hozalski. Kinetics of Haloacetic Acid Reactionswith Fe(0). Environmental Science & Technology. 2004,38(24): 6881~6889
2 R. J. Bull, F. C. Kopfler. Health Effects of Disinfectants and Disinfection By-products. AWWARF, Denver, 1991
3 K. Verschueren. Handbook of Environmental Data on Organic Chemicals. Van Nostrand Reinhold, 1983
4 B. L. Dvorak, D. F. Lawler. Selecting Among Physical/Chemical Processes for Removing Synthetic Oganics from Water. Water Environment Research. 1993,65(7): 827~838
5刘毅慧.水中氯代有机物催化还原脱氯的研究.大连理工大学博士学位. 1999: 13~19 20~21
6赵毅.多氯联苯催化转移氢化脱氯的研究.环境化学. 1994,13(4): 328~330
7 D. P. Sinatar, C. G. Schreier, C. Chi-Su, M. Reinhard. Treatment of 1,2-dibromo-3-chloropropane and Nitrate-contaminated Water with Zero-valentIron or Hydrogen/Palladium Catalysts. Water Research. 1996,30(10): 2315~2322
8 M. R. Kriegman-King, M. Reinhard. Transformation of Carbon Tetrachloride by Pyrite in Aqueous Solution. Environmental Science & Technol. 1994,28(4): 692~700
9 P. D. Hooker, K. J. Klaubunde. Destructive Adsorption of Carbon Tetrachloride on Iron(Ⅲ) Oxide. Environmental Science & Technology. 1994,28(7): 1243~1247
10 M. Erbs, H. C. B. Hansen, C. E. Olsen.Reductive Dechlorination of Carbon Tetrachloride Using Iron(Ⅱ)Iron(Ⅲ) Hydroxide Sulfate(green rust)．Environmental Science & Technology. 1999,33(2): 307~311
11 E. C. Butle, K. F. Hayes. Effects of Solution Composition and pH on the Reductive Dechlorination of Hexachloroethane by Iron Sulfide. Environmental Science & Technology. 1998,32(9): 1276~1284
12卫建军.纳米级Pd/Fe双金属对水中氯酚的催化脱氯研究.浙江大学博士学位. 2004: 8~10 14~18 20~21
13 R. M. Hozalski, L. Zhang, W. A. Arnold. Reduction of Haloacetic Acids by Fe：Implications for Treatment and Fate. Environmental Science & Technology.2001,35(11): 2258~2263
14周红艺等.含铁化合物对有机氯化物的脱氯处理技术研究.环境污染治理技术与设备. 2002,3(1): 52~56
15周红艺.钯/铁双金属体系对氯代芳烃的催化脱氯研究.浙江大学博士学位2003: 16
16全燮,杨凤林,薛大明,赵雅芝,冯文国,苍郁.钯-铁催化还原法对水中二氯乙烯的快速脱氯研究.人连理工大学学报. 1997,37(1): 46~48 107
17 R. Koch. Galvanic Action Water Purifier. U. S.–Pat. 1968. 3392102-A
18 E. K. Wilson. Zero-valent Metals Provide Possible Solution to Groundwater Problems. Chemical and Environment. 1995,73(21): 19~22
19 R. Muftikian, Q. Fernando, N. Korte. A Method for the Rapid Dechlorination of Low Molecular Weight Chlorinated Hydrocarbons in Water. Water Research. 1995, 29(10): 2434~2439
20全燮,刘会娟,杨凤林,薛大明,赵雅芝.二元金属体系对水中多氯有机物的催化还原脱氯特性.中国环境科学. 1998,18(4): 333~336
21 N. E. Korte, J. L. Zutman, R. M. Schlosser. Field Application of Palladized Iron for the Dechlorination of Trichloroethene. Waste Management. 2000,20(8): 687~694
22何小娟,汤鸣皋,沈照理,崔卫华,徐鹏. Ni/Fe双金属对PCE脱氯影响效果因素研究.地球科学-中国地质大学学报. 2003,28(3): 337~340
23何小娟,汤鸣皋,李旭东,徐鹏.镍/铁和铜/铁双金属降解四氯乙烯的研究.环境化学. 2003,22(4): 334~339
24 Y. H. Liu, F. L. Yang, P. L. Yue, G. H. Chen. Catalytic Dechlorination of Chlorophenols in Water by Palladium/Iron. Water Research. 2001,35(8): 1887~1890
25 L, J, Graham, G. Jovanovic. Dechlorination of P-chlorophenol on a Pd/FeCatalyst in A Magnetically Stabilized Fluidized Bed：Implications for Sludge and Liquid Remediation. Chemical Engineering Science. 1999,54(15-16): 3085~3093
26 Y. H. Kim, E. R. Carraway. Dechlorination of Pentachlorophenol by Zero Valent Iron and Modified Zero Valent Irons. Environmental Science & Technology.2000,34(10): 2014~2017
27 J. G. Doyle, T. Miles, E. Parker. Quantification of Total Polychlorinated Biphenylby Dechlorination to Biphenyl by Pd/Fe and Pd/Mg Bimetallic Particles. Microchemical Journal. 1998,60(3): 290~295
28 M. D. Engelmann, R. Hutcheson, K. Henschied, R. Neal, I. F. Cheng. Simultaneous Determination of Total Polychlorinated Biphenyl and Dichlorodiphenyltrichloroethane(DDT) by Dechlorination with Fe/Pd and Mg/Pd Bimetallic Particles and Flame Ionization Detection Gas Chromatography.Microchemical Journal. 2003,74(1): 19~25
29 W. X. Zhang, C. B. Wang, H. L. Lien. Treatment of Chlorinated Organic Contaminants with Nanoscale Bimetallic Particles. Catalysis Today. 1998,40(4): 387~395
30 H. L. Lien, W. X. Zhang. Transformation of Chlorinated Methanes by Nanoscale Iron Particles. Journal of Environmental Engineering. 1999,125(11): 1042~1047
31 H. L. Lien，W. X. Zhang. Nanoscale Iron Particles for Complete Reduction of Chlorinated Ethenes. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2001,191(1): 97~105.
32 D. W. Elliott, W. X. Zhang. Field Assessment of Nanoscale Bimetallic Particles for Groundwater Treatment. Environmental Science Technology. 2001,35(24): 4922~4926
33 S. Kidambi, M. L. Bruening, Multilayered Polyelectrolyte Films Containing Palladium Nanoparticles: Synthesis, Characterization, and application in Selective Hydrogenation. Chemistry of Materials. 2005,17(2): 301~307
34 L. Wu, M. Shamsuzzoha, S. M. C. Ritchie. Preparation of Cellulose Acetate Supported Zero-Valent Iron Nanoparticles for the Dechlorination of Trichloroethylene in Water. Journal of Nanoparticle Research. 2005,7(4-5): 469~476
35 J. K. Gotpagar, E. A. Grulke, T. Tsang, D. Bhattacharyya. Reductive Dehalogenation of Trichloroethylene Using Zero-Valent Iron. Environmental Progress. 1997,16(2): 137~143
36 F. Li, C. Vipulanandan, K. K. Mohanty. Microemulsion and Solution Approaches to Nanoparticle Iron Production for Degradation of Trichloroethylene. Colloids and Surfaces. A: Physicochemical and Engineering Aspects. 2003,223(1): 103~112
37 L. F. Wu, S. M. C. Ritchie. Removal of Trichloroethylene from Water byCellulose Acetate Supported Bimetallic Ni/Fe Nanoparticles. Chemosphere. 2006,63(2): 285~292
38 J. Xu, D. Bhattacharyya. Membrane-based Bimetallic Nanoparticles for Environmental Remediation: Synthesis and Reactive Properties. Environmental Progress. 2005,24(4): 358~366
39 T. C. Wang, M. F. Rubner, R. E. Cohen. Polyelectrolyte Multilayer Nanoreactors for Preparing Silver Nanoparticle Composites: Controlling Metal Concentration and Nanoparticle Size. Langmuir. 2002,18(8): 3370~3375.
40 J. Xu, D. Bhattacharyya. Fe/Pd Nanoparticle Immobilization in Microfiltration Membrane Pores: Synthesis, Characterization, and Application in the Dechlorination of Polychlorinated Biphenyls. Industrial Engineering Chemistry Research. 2007,46(8): 2348~2359.
41 L. J. Matheson, P. Q. Tratnyek. Reductive Dehalogenation of Chlorinated Methanes by Iron Metal. Environmental Science & Technology. 1994,28(12): 2045~2053
42 T. L. Johnson, M. M. Scherer, P. G. Tratnyek. Kinetics of Halogenated Organic Compound Degradation by Iron Metal. Environmental Science & Technology. 1996,30(8): 2634~2640.
43 R. Weerasooriya, B. Dharmasena. Pyrite-assisted Degradation of Trichloroethene. Chemosphere. 2001,42(4): 389~396
44 J. Xu, A. Dozier, D. Bhattacharyya. Synthesis of Nanoscale Bimetallic Particlesin Polyelectrolyte Membrane Matrix for Reductive Transformation of Halogenated Organic Compounds. Journal of Nanoparticle Research. 2005,7(4-5): 449~467
45周洁.聚偏氟乙烯膜的亲水改性及处理低浓度含油废水的研究.南京理工大学硕士学位论文. 2005: 10~19
46黎雁,吕晓龙.聚偏氟乙烯多孔膜的改性研究进展.天津工业大学学报. 2001,20(5): 74~78
47吴万国,丁音琴,黄清明.纳米材料晶粒鉴定方法的研究.福州大学学报(自然科学版). 2003,31(1):49～51
48周红艺,徐新华,汪大翚.钯/铁双金属对水中氯苯的催化脱氯研究.浙江大学学报(工学版) . 2003,37(3): 345~349
49 L. Zhang, W. A. Arnold, R. M. Hozalski. Kinetics of Haloacetic Acid Reactionswith Fe(0). Environmental Science & Technology. 2004,38(24): 6881~6889