Please use this identifier to cite or link to this item:
標題: 奈米零價鐵鈀還原降解五氯酚之研究
Reduction of Pentachlorophenol by Nanoscale Pd0/Fe0 Bimetallic Particles
作者: 陳孟宜
Chen, Meng-Yi
關鍵字: pentachlorophenol;五氯酚;nanoscale Palladium/iron;degradation;奈米零價鐵鈀;降解
出版社: 土壤環境科學系所
引用: Agrawal, A., and P.G. Tratnyek. 1996. Reduction of nitroaromatic compounds by zero-valent iron metal. Environ. Sci. Technol. 30:153-160. Agriculture Canada. 1987. Pentachlorophenol discussion document. Ottawa, Ontario: Pesticides Directorate. Benitez, F.J., J.L. Acero, F.J. Real, and J. Garcia. 2003. Kinetics of photodegradation and ozonation of pentachlorophenol. Chemosphere. 51:651-662. Benjamin, M.M. 2002. Water chemistry. McGraw-Hill Company. New York. Blowes, D.W., C.J. Ptacek, S.G. Benner, C.W.T. McRae, T.A. Bennett, and R.W. Puls. 2000. Treatment of inorganic contaminants using permeable reactive barrier. J. Contam. Hydrol. 45:123-137. Brezonik, P.L. 1994. Chemical kinetics and process dynamics in aquatic systems. Lewis Publishers. Boca Raton. Chen, J.L., S.R.A. Abed, J. Al-Ryanb, and Z. Li. 2001. Effect of pH on the dechlorination of trichloroethylene by zero-valent iron. J. Hazard. Mater. B 83:243-254. Chung, F.H., and D.K. Smith. 2000. Industrial application of x-ray diffraction. Marcel Dekker. New York. Cortes, D., J. Barrrios-Gonzalez, and A. Tomasini. 2001. Pentachlorophenol tolerance and removal by Rhizopus nigricans in solid-state culture. Process biochem. 37:881-884. Davis, A., J. Campbell, C. Gilbert, M.V. Ruby, M. Benett, and S. Tobin. 1994. Attenuation and biodegradation of chlorophenols in ground water at a former wood treating facility. Ground Water. 32:248-257. Domdek, T., E. Dolan, J. Schultz, and D. Klarup. 2001. Rapid reductive dechlorination of atrazine by zero-valent iron under acidic conditions. Environ. Pollut. 111:21-27. Environmental Protection Administration, R.O.C. 2008. Fein, J.B. 1996. The effect of aqueous metal-chlorophenolate complexation on contaminant transport in groundwater systems. Appl. Geochem. 11:735-774. Fisher, B. 1991. Pentachlorophenol: toxicology and environmental fate. J. Pesticide Reform. 11:2-5. Freire, P.F., V. Labrador, J.M.P. Martin, and M.J. Hazen. 2005. Cytotoxic effects in mammalian vero cells exposed to pentachlorophenol. Toxicology. 210:37-44. Gerhard, I., M. Derner, and B. Runnebaum. 1991. Prolonged exposure to wood preservatives induces endocrine and immunologic disorders in women. Am. J. Obstet. Gynecol. 165:487-488. Gramham, L.J., and G. Jovanovic. 1999. Dechlorination of p-chlorophenol on a Pd/Fe catalyst in a magnetically stabilized fluidized bed: implications for sludge and liquid remediation. Chem. Eng. Sci. 54:3085-3093. Guettaï, N., and H.A. Amar. 2005. Photocatalytic oxidation of methyl orange in presence of titanium dioxide in aqueous suspension. Part Ⅱ: kinetics study. Desalination. 185:439-448. Hattemer-Frey, H.A., and C.C. Travis. 1989. Pentachlorophenol: environmental partitioning and human exposure. Arch. Environ. Contam. Toxicol. 18:482-489. He, Y., J. Xu, H. Wang, and Y. Wu. 2007. Generalized models for prediction of pentachlorophenol dissipation dynamics in soils. Environ. Poll. 147:343-349. Hernandez, R., M. Zappi, and C.H. Kuo. 2004. Chloride effect on TNT degradation by zerovalent iron or zinc during water treatment. Environ. Sci. Technol. 37:2905-2912. Huang, C.P., H.W. Wang, and P.C. Chiu. 1998. Nitrate reduction by metallic iron. Wat. Res. 32:2257-2264. Huang, G.L., H. Xiao, J. Chi, W.Y. Shiu, and D. Mackay. 2000. Effects of pH on the aqueous solubility of selected chlorinated phenols. J. Chem. Eng. Data. 45:411-414. Johnson, T.L., M.M. Scherer, and P.G. Tratnyek. 1996. Kinetics of halogenated organic compound degradation by iron metal. Environ. Sci. Technol. 30:2634-2640. Joo, S.H., and D. Zhao. 2008. Destruction of lindane and atrazine using stabilized iron nanoparticles under aerobic and anaerobic conditions: effects of catalyst and stabilizer. Chemosphere. 70:418-425. Jovanovic, G.N., P.Z. Plazl, P. Sakrittichai, and K.A. Khaldi. 2005. Dechlorination of p-chlorophenol in a microreactor with bimetallic Pd/Fe catalyst. Ind. Eng. Chem. Res. 44:5099-5106. Kim, Y.H., and E.R. Carraway. 2000. Dechlorination of pentachlorophenol by zero valent irons. Environ. Sci. Technol. 34:2014-2017. Kim, Y.H., and E.R. Carraway. 2003. Dechlorination of chlorinated phenols by zero valent zinc. Environ. Technol. 24:1455-1463. Korte, N.E., J.L. Zutman, R.M. Schlosser, L. Liang, B. Gub, and Q. Fernando. 2000. Field application of palladized iron for the dechlorination of trichloroethene. Waste Manag. 20:687-694. Lai, K.C.K., and I.M.C. Lo. 2008. Removal of chromium(Ⅵ) by acid-washed zero-valent iron under various groundwater geochemistry conditions. Environ. Sci. Technol. 42:1238 -1244. Laidler, K.J. 1965. Chemical kinetics. McGraw-Hill. New York. Lange, C.C., B.J. Schneider, and C.S. Orser. 1996. Verification of the role of PCP 4-monooxygenase in chlorine elimination from pentachlorophenol by Flavobacterium sp. strain ATCC 39723. Biochem. Biophys. Res. Commun. 219:146-149. Li, C., and M.Z. Hoffman. 1999. One-electron redox potentials of phenols in aqueous solution. J. Phys. Chem. B. 103:6653-6656. Lien, H.L., and W. Zhang. 2004. Effect of palladium on the reductive dechlorination of chlorinated ethylenes with nanoscale Pd/Fe particles. Water Sci. Technol. Wat. Sup. 4:297-303. Lien, H.L., and W.X. Zhang. 2005. Hydrodechlorination of chlorinated ethanes by nanoscale Pd/Fe bimetallic particles. J. Enviorn. Eng. 131:4-10. Lien, H.L., and W.X. Zhang. 2007. Nanoscale Pd/Fe bimetallic particles: catalytic effects of palladium on hydrodechlorination. Appl. Catal. B: Environ. 77:110-116. Lin, K.S., N.B. Chang, and T.D. Chuang. 2008. Fine structure characterization of zero-valent iron nanoparticles for decontamination of nitrites and nitrates in wastewater and groundwater. Sci. Technol. Adv. Mater. 9:1-9. Liu, Y., F. Yang, P.L. Yue, and G. Chen. 2001. Catalytic dechlorination of chlorophenols in water by palladium/iron. Wat. Res. 35:1887-1890. Liu, Y., T. Phenrat, and G.V. Lowry. 2007. Effect of TCE concentration and dissolved groundwater solutes on NZVI-promoted TCE dechlorination and H2 evolution. Environ. Sci. Technol. 41:7881-7887. Lowry, G.V., and K.M. Johnson. 2004. Congener-specific dechlorination of dissolved PCBs by microscale and nanoscale zerovalent iron in a water/methanol solution. Environ. Sci. Technol. 38:5208-5216. Lu, M.C., Y.F. Chang, I.M. Chen, and Y.Y Huang. 2005. Effect of chloride ions on the oxidation of aniline by Fenton's reagent. J. Environ. Manage. 75:177-182. Marshall, W.D., A. Kubatova, A.J.M. Lagadec, D.J. Miller, and S.B. Hawthorne. 2002. Zero-valent metal accelerators for the dechlorination of pentachlorophenol (PCP) in subcritical water. Green Chem. 4:17-23. Matheson, L.J., and P.G. Tratnyek. 1994. Reductive dehalogenation of chlorinated methanes by iron metal. Environ. Sci. Technol. 28:2045-2053. Morales, J., R. Hutcheson, and I. F. Cheng. 2002. Dechlorination of chlorinated phenols by catalyzed and uncatalyzed Fe(0) and Mg(0) particles. J. Hazard. Mater. B 90:97-108. Morel, F.M.M., and J.G. Hering. 1993. Principles and applications of aquatic chemistry. Wiley. New York. O'Loughlin, E.J., K.M. Kemner, and D.R. Burris. 2003. Effect of AgI, AuIII, and CuII on the reductive dechlorination of carbon tetrachloride by green rust. Environ. Sci. Technol. 37:2905-2912. Orth, W.S., and R.W. Gillham. 1996. Dechlorination of trichloroethene in aqueous solution using Fe0. Environ. Sci. Technol. 30:66-71. Pallerla, S., and R.P. Chambers. 1998. Reactor development for biodegradation of pentachlorophenol. Catal. today. 40:103-111. Patel, U.D., and S. Suresh. 2008. Effect of solvent, pH, salts and resin fatty acids on the dechlorination of pentachlorophenol using magnesium-silver and magnesium-palladium bimetallic systems. J. Hazard. Mater. 156:308-316. Phillips, D.H., B. Gu, D.B. Watson, Y. Roh, L. Liang, and S.Y. Lee. 2000. Performance evaluation of a zerovalent iron reactive barrier: mineralogical characterizatios. Environ. Sci. Technol. 34:4169-4176. Rajagopal, V.K., and D.R. Burris. 1999. Reduction of 1,2-dibromoethane in the presence of zero-valent iron. Environ. Toxicol. Chem. 18:1779-1782. Rao, K.R. 1987. Pentachlorophenol: chemistry, pharmacology and environmental toxicology. plenum. New York. Satapanajaru, T., P. Anurakpongsatorn, P. Pengthamkeerati, and H. Boparai. 2008. Remediation of atrazine-contaminated soil and water by nano zerovalent iron. Water. Air. Soil. Pollut. 192:349-359. Scheutz, C., K. Winther, and P. Kjeldsen. 2000. Removal of halogenated organic compounds in landfill gas by top covers containing zero-valent iron. Environ. Sci. Technol. 34:2557-2563. Schwarzenbach, R.P., P.M. Gschwend, and D.M. Imboden. 2003. Environmental organic chemistry. Wiley, 2nd. New Jersey. Shih, Y.H., and C.Y. Hsu. 2008. Reduction of hexachlorobenzene by nanoscale zerovalent iron: kinetics, pH effect, and dechlorination mechanism. (Submitted to Environ. Sci. Technol.) Shih, Y.H., and C.Y. Hsu. 2008. The effect of ions on dechlorination of hexachlorobenzene by nanoscale zero-valent iron. (Submitted to Environ. Sci. Technol.) Shih, Y.H., Y.C. Chen, M.Y. Chen, Y.T. Tai, and C.P. Tso. 2009. Dechlorination of hexachlorobenzene by using nanoscale Fe and nanoscale Pd/Fe bimetallic particles. Colloid. Surf. A: Physicochem. Eng. Asp. 332:84-89. Song, H., and E.R. Carraway. 2005. Reduction of chlorinated ethanes by nanosized zero-valent iron: kinetics, pathways, and effects of reaction conditions. Environ. Sci. Technol. 39:6237-6245. Speight, J.G. 2005. Lange's handbook of chemistry. McGraw-Hill, 6th. New York. Stanmore, B.R. 2004. The formation of dioxins in combustion systems. Combust. Flame. 136:398-427. Stumm, W., and J.J. Morgan. 1981. Aquatic chemistry. Wiley. New York. Stumm, W., and J.J. Morgan. 1996. Aquatic chemistry: chemical equilibrium and rates in natural waters. Wiley, 3rd. New York. Su, C., and D.L. Suarez. 1997. In situ infrared speciation of adsorbed carbonate on aluminum and iron oxides. Clays Clay Miner. 45:814-825. Su, C., and R.W. Puls. 2001. Arsenate and arsenite removal by zerovalent iron: kinetics, redox transformation, and implications for in situ groundwater remediation. Environ. Sci. Technol. 35:1487 -1492. Su, C., and R.W. Puls. 2004. Nitrate reduction by zerovalent iron: effect of formate, oxalate, citrate, chloride, sulfate, borate, and phosphate. Environ. Sci. Technol. 38:2715-2720. Tee, Y.H., E. Grulke, and D. Bhattacharyya. 2005. Role of Ni/Fe nanoparticle composition on the degradation of trichloroethylene from water. Ind. Eng. Chem. Res. 44:7062-7070. The physical and theoretical chemistry laboratory oxford university-chemical and other safety information. 2008. Thomas, J.M. 2006. Single-step treatment of 2,4-dinitrotoluene via zero-valent metal reduction and chemical oxidation. Masters Tehsis. Mississippi State University. Uotila, J.S., V.H. Kitunen, T. Saastamoinen, T. Coote, M.M. Haggblom, and M. Salkinoja-Salonen. 1992. Characterization of aromatic dehalogenase of Mycobacterium fortuitum CG-2. J. Bacteriol. 174:5669-5675. Wang, C.B., and W.X. Zhang. 1997. Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs. Environ. Sci. Technol. 31:2154-2156. Wang, H., V. Marjomaki, V. Ovod, and M.S. Kulomaa. 2002. Subcellular localization of pentach. Subcellular localization of pentachlorophenol 4-monooxygenase in Sphingobium chlorophenolicum ATCC 39723. Biochem. Biophys. Res. Commun. 299:703-709. Wei, J., X. Xu, Y. Liu, and D. Wang. 2006. Catalytic hydrodechlorination of 2,4-dichlorophenol over nanoscale Pd/Fe: reaction pathway and some experimental parameters. Water Res. 40: 348-354. Wild, S.R., S.J. Harrad, and K.C. Jone. 1993. Chlorophenols in digested UK sewage sludges. Water Res. 27:1527-1534. Wust, W.F., R. Kober, O. Schlicher, and A. Dahmke. 1999. Combined zero- and first-order kinetic model of the degradation of TCE and cis-DCE with commercial iron. Environ. Sci. Technol. 33:4304-4309. Xu, X., H. Zhou, P. He, and D. Wang. 2005. Catalytic dechlorination kinetics of p-dichlorobenzene over Pd/Fe catalysts. Chemosphere. 58:1135-1140. Yuan, T., and W.D. Marshall. 2002. Dechlorination of pentachlorophenol in supercritical carbon dioxide with zero-valent palladium-magnesium bimetallic mixture. J. Environ. Monit. 4:452-457. Zawaideh, L.L., and T.C. Zhang. 1998. The effects of pH and addition of an organic buffer (HEPES) on nitrate transformation in Fe0-water systems. Wat. Sci. Tech. 38:107-115. Zelles L, I. Scheunert, and F. Korte. 1985. Side effects of some pesticides on non-target soil microorganisms. J. Environ. Sci. Health. B 20: 457-488. Zhang, H., M. Jiang, Z. Wang, and F. Wu. 2007. Decolorisation of CI reactive black 8 by zero-valent iron powder with/without ultrasonic irradiation. Color. Technol. 123:203-208. Zhang, L., and A. Manthiram. 1997. Chains composed of nanosize metal particles and identifying the factors driving their formation. Appl. Phys. Lett. 70:2469-2471. Zhang, W.X. 2003. Nanoscale iron particles for environmental remediation: a overview. J. Nanopart. Res. 5:323-332. Zhang, W.X., C.B. Wang, and H.L. Lien. 1998. Treatment of chlorinated organic contaminants with nanoscale bimetallic particles. Catal. Today. 40:387-395. Zhu, B.W., and T.H. Lim. 2007. Catalytic reduction of chlorobenzenes with Pd/Fe nanoparticles: reactive sites, catalyst stability, particle aging, and regeneration. Environ. Sci. Technol. 41:7523-7529.
Pentachlorophenol (PCP), one of persistent organic pollutant (POP) and also a carcinogenic compound, has been used widely as wood preservative and pesticides in the past. Due to the improper storage and disposal of these persistent organic pollutants, several POP contaminated sites were found in the world, especially a PCP contaminated site in Taiwan. Nanoscale zerovalent metal particles were developed to in-situ chemically degrade poly-halogenated aromatic contaminants.
Nanoscale Pd0/Fe0 particles we synthesized were used to evaluate the potential of Pd0/Fe0 nanoparticles for the remediation the PCP contaminated sites. The effects of nanoscale Pd0/Fe0 dosage, palladium loading, PCP concentrations, and aqueous parameters such as different concentration of various common cations and anions, temperature, and pH, on the degradation of PCP were performed. And the removal experiments of PCP in PCP contaminated soil and Lukang soil were investigated.
The increase of nanoscale Pd0/Fe0 dosage results in the increase in PCP degradation rate and efficiency due to more Pd0/Fe0 surface to reduce PCP. With the increase of the palladium loading percentage from 0.02 wt % to 0.054 wt %, PCP degradation rates increased but the degradation rate slightly decreased with the increase of the palladium loading percentage from 0.054 wt % to 0.13 wt %. It seems a common characteristic for catalyst. The effect of initial PCP concentrations on the removal rate can be described by a surface kinetic model, Langmuir-Hinshelwood model. The estimated activation energy of the dechlorination reactions of 29 kJ/mol indicates that the degradation of PCP on Pd0/Fe0 nanoparticle is a surface-control mechanism.
The effects of common cations and anions on the degradation of PCP with Pd0/Fe0 nanoparticles were needed to be studied. Common groundwater anions inhibited PCP reduction in increasing order of Cl- < HCO3- < SO42- < HPO42- < NO3-, which is generally consistent with their affinity to form complexes with iron oxide except NO3- and HCO3-. Generally, the inhibition effect increased with the increase of anion concentrations. Nitrate may compete electrons offered from iron with PCP to reduce other nitrogen species. The smallest pH variation before and after experiments indicates that HCO3- has pH buffer capacity.
In the presence of sulfate, which can cause for inhibition, cation Na+ was proposed to have no influence the degradation efficiencies of PCP and used as a reference. Cations Mg2+, Cu2+, Ni2+ and Fe3+ could facilitate the degradation efficiencies of PCP with nanoscale Pd0/Fe0 particles in increasing order of Cu2+ < Mg2+ < Fe3+ < Ni2+. With chloride ions, the smallest effect in our anions, the decrease trend of PCP degradation for these cations is similar, except Cu2+. Moreover, Ni2+ could increase the degradation kinetics and efficiency of PCP with Pd0/Fe0 nano-particles although either sulfate or chloride ions inhibit the degradation behaviors.
The increase of concentration of soil solution showed a negative effect on the degradation rate constants of PCP by nanoscale Pd0/Fe0 particles. Soil solution containing common anions may inhibit the degradation. The anions in soil solutions would form iron-complex or metal oxides precipitation on nanoscale Pd0/Fe0 particles to decrease the surface reactivity.
According to the instant occurrence of degraded byproducts, tetrachlorophenols, trichlorophenols, dichlorophenols, chlorophenols, and phenol during the reaction, multiple dechlorination process is proposed for the PCP degradation reaction on the nanoscale Pd0/Fe0 particles. The chlorine atom at the ortho and meta positions can be more easily dechlorinated than that at para position on PCP. It results from the steric effect of chloride on PCP structure.
An efficient degradation of the PCP with nanoscale Pd0/Fe0 particles in soils was performed in this study. The degradation efficiency and kinetics of PCP in Lukang soil are less than these in PCP contaminated soil due to the higher nitrate concentration and higher soil organic carbon in Lukang soil than PCP contaminated soil. Nitrate ions inhibit the reduction of PCP. The low degradation efficiency could also result from larger adsorption of PCP in Lukang soil. The colloids in soils may also decrease the degradation efficiency in the application of removal of PCP with nanoscale Pd0/Fe0 particles so a higher amount of Pd/Fe nanoparticles was used in soil than in solution.
These better understandings can facilitate the remediation design and the prediction of treatment efficiency of PCP with nanoscale Pd0/Fe0 particles. Nanoscale Pd0/Fe0 particles could be a potential remediation agent for PCP contaminated sites because their rapid removal reactions of PCP occur in soils and groundwater and an excess of the nanoscale Pd0/Fe0 particles in the soils can provide an extra reducing power to reduce the target polyhalogenated aromatic compounds of PCP.

五氯酚 (pentachlorophenol, PCP) 過去使用於木材保護劑與殺蟲劑,其為持久性之有機污染物 (persistent organic pollutants, POP) 且具致癌性。由於不適當儲存與廢棄這些持久性有機污染物,世界已有許多POP污染場址,台灣已發現PCP污染場址。而奈米零價鐵鈀 (palladium/iron, Pd0/Fe0) 顆粒之技術已發展於現地化學還原含鹵素有機污染物。
此研究以批次實驗系統應用自行合成之奈米Pd0/Fe0移除PCP,評估以供復育污染場址之潛力。由於增加奈米Pd0/Fe0劑量使其具較多之Pd0/Fe0表面以還原PCP,故其降解速率提高。奈米Pd0/Fe0顆粒之Pd重量百分比於0.02 wt %至0.054 wt %之間,則增加Pd重量百分比則會提高PCP之降解速率,但若增加Pd之重量百分比至 0.13 wt %,則會降低PCP之降解速率。PCP初始濃度之影響可以Langmuir-Hinshelwood模式描述,另外經計算求得之活化能為29 kJ/mol,此結果顯示利用奈米Pd0/Fe0降解PCP為一表面控制反應。
地下水中常見之陰離子會抑制PCP之降解效率,其抑制的順序依序為Cl- < HCO3- < SO42- < HPO42- < NO3-。除了NO3-與HCO3-之外,此抑制順序與這些陰離子與鐵氧化物產生複合物之親合力順序相符,抑制程度隨其濃度增加而增加。而NO3-會與PCP競爭電子而使其還原成其他含氮化合物,所以抑制PCP之降解效率最顯著。HCO3-因其具有pH緩衝能力而減少抑制PCP之降解效率。
在SO42-為背景陰離子之情況下,因如前所述,SO42-會抑制奈米Pd0/Fe0降解PCP,又因Na+之高還原電位,所以Na+應不影響奈米Pd0/Fe0降解PCP,可作為比較之基準。所以相較於相同濃度之下,Mg2+、Cu2+、Ni2+與Fe3+則可促進PCP之降解效率,其促進之順序依序為Cu2+ < Mg2+ < Fe3+ < Ni2+。此外,Ni2+即使未扣除SO42-之影響,其亦會促進PCP之降解效率。而在以Cl-為背景陰離子之情況下,相同地以Cl-為抑制奈米Pd0/Fe0降解PCP之原因,所以NaCl對利用奈米Pd0/Fe0降解PCP的影響作為比較基準。Mg2+、Ni2+與Fe3+則可促進PCP之降解效率,其促進之順序依序為Mg2+ < Fe3+ < Ni2+。但Cu2+會抑制PCP之降解效率。此外,Ni2+即使未扣除Cl-之影響,其亦會促進PCP之降解效率。
其他識別: U0005-2512200815104000
Appears in Collections:土壤環境科學系

Show full item record

Google ScholarTM


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.