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Nanoporous zero-valent iron

Published online by Cambridge University Press:  01 December 2005

Jiasheng Cao ,
Patrick Clasen  and
Wei-xian Zhang
Jiasheng Cao
Affiliation:
Center for Advanced Materials and Nanotechnology, Department of Civil and Environmental Engineering, Lehigh University, Bethlehem, Pennsylvania 18015
Patrick Clasen
Affiliation:
Center for Advanced Materials and Nanotechnology, Department of Civil and Environmental Engineering, Lehigh University, Bethlehem, Pennsylvania 18015
Wei-xian Zhang*
Affiliation:
Center for Advanced Materials and Nanotechnology, Department of Civil and Environmental Engineering, Lehigh University, Bethlehem, Pennsylvania 18015
*
a)Address all correspondence to this author. e-mail: [email protected]
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Abstract

Hollow and nanoporous particles of zero-valent iron (ZVI) were prepared with template-directed synthesis. Polymer resin beads (0.4 mm diameter) were coated with nanoscale iron particles by reductive precipitation of ferrous iron [Fe(II)] with sodium borohydride. The resin was calcinated at 400 °C to produce hollow and nanoporous iron spheres. The nanoporous iron oxides were then reduced to metallic iron by hydrogen at 500 °C. Scanning electron microscope images of the reduced iron spheres showed that the particles were hollow. The shell thickness was approximately 5 μm and highly porous. Brunauer–Emmett–Teller specific surface area was 2100 m2/kg. In comparison, the theoretical specific surface area of solid iron particles of the same size is just 1.9 m2/kg. Batch tests showed that the surface area normalized reactivity of the porous particles were 14–31% higher than microscale iron particles with similar surface areas for the transformation of hexavalent chromium [Cr(VI)], azo dye Orange II {4-[(2-hydroxyl-1-naphthalenyl)azo]-benzenesulfonic acid monosodium}, and trichloroethene. The combined performance enhancement (larger surface area and higher surface activity) is significant (>1200 times).

Keywords

Chemical reactivityMetalPorosity
Type
Articles—Energy and The Environment Special Section
Information
Journal of Materials Research , Volume 20 , Issue 12 , December 2005 , pp. 3238 - 3243
Copyright
Copyright © Materials Research Society 2005

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References

REFERENCES

1.Gillham, R.W. and O’Hannesin, S.F.: Enhanced degradation of halogenated alipahtics by zero-valent iron. Ground Water 32, 958 (1994).CrossRefGoogle Scholar
2.Starr, R.C. and Cherry, J.A.: In-situ remediation of contaminated ground-water: The funnel and gate system. Ground Water 32, 465 (1994).Google Scholar
3.LaGrega, M.D., Buckingham, P. and Evans, J.C.: Hazardous Waste Management, 2nd ed. (McGraw-Hill, New York, 2001).Google Scholar
4.Gilbert, O., de Pablo, J., Cortina, J.L. and Ayora, C.: Evaluation of municipal compost/limestone/iron mixtures as filling material for permeable reactive barriers for in-situ acid mine drainage treatment. J. Chem. Technol. Biot. 78, 489 (2003).CrossRefGoogle Scholar
5.Appleton, E.L.: A nickel-iron wall against contaminated groundwater. Environ. Sci. Technol. 30, 536A (1996).Google Scholar
6.Barcelona, M.J. and Xie, G.: In situ lifetimes and kinetics of a reductive whey barrier and an oxidative ORC barrier in the subsurface. Environ. Sci. Technol. 35, 3378 (2001).CrossRefGoogle Scholar
7.Scherer, M.M., Richter, S., Valentine, R.L. and Alvarez, P.J.: Chemistry and microbiology of permeable reactive barriers for in situ groundwater clean up. Crit. Rev. Environ. Sci. Technol. 30, 363 (2000).CrossRefGoogle Scholar
8.Puls, R.W., Blowes, D.W. and Gillham, R.W.: Long-term performance monitoring for a permeable reactive barrier at the U.S. Coast Guard Support Center, Elizabeth City, North Carolina. J. Hazard. Mater. 68, 109 (1999).Google Scholar
9.Wang, C. and Zhang, W.X.: Nanoscale iron particles for reductive dechlorination of PCE and PCBs. Environ. Sci. Technol. 31, 2154 (1997).CrossRefGoogle Scholar
10.Lien, H. and Zhang, W.X.: Complete dechlorination of chlorinated ethenes with nanoparticles. Colloids Surf. A 191, 97 (2001).Google Scholar
11.Arnold, W.A. and Roberts, A.L.: Pathways and kinetics of chlorinated ethylene and chlorinated acetylene reaction with Fe(0) particles. Environ. Sci. Technol. 34, 1794 (2000).CrossRefGoogle Scholar
12.Siantar, D.P., Schreier, C.G., Chou, C.S. and Reinhard, M.: Treatment of 1,2-dibromo-3-chloropropane and nitrate-contaminated water with zero-valent iron or hydrogen/palladium catalysts. Water Res. 30, 2315 (1996).CrossRefGoogle Scholar
13.Xu, Y. and Zhang, W.X.: Subcolloidal Fe/Ag particles for reductive dehalogenation of chlorinated benzenes. Ind. Eng. Chem. Res. 39, 2238 (2000).CrossRefGoogle Scholar
14.Furukawa, Y., Kim, J-W., Watkins, J. and Wilkin, R.T.: Formation of ferrihydrite and associated iron corrosion products in permeable reactive barriers of zero-valent iron. Environ. Sci. Technol. 36, 5469 (2002).CrossRefGoogle ScholarPubMed
15.Elliott, D.W. and Zhang, W.X.: Field assessment of nanoparticles for groundwater treatment. Environ. Sci. Technol. 35, 4922 (2001).CrossRefGoogle ScholarPubMed
16.Morrison, S.J., Metzler, D.R. and Carpenter, C.E.: Uranium precipitation in a permeable reactive barrier by progressive irreversible dissolution of zerovalent iron. Environ. Sci. Technol. 35, 385 (2001).CrossRefGoogle Scholar
17.Cheng, I.F., Muftikian, R., Fernando, Q. and Korte, N.: Reduction of nitrate to ammonia by zero-valent iron. Chemosphere 35, 2689 (1997).Google Scholar
18.Weber, E.J.: Iron-mediated reductive transformations: Investigation of reaction mechanism. Environ. Sci. Technol. 30, 716 (1996).CrossRefGoogle Scholar
19.Deng, B.L., Campbell, T.J. and Burris, D.R.: Hydrocarbon formation in metallic iron/water systems. Environ. Sci. Technol. 31, 1185 (1997).Google Scholar
20.Matheson, L.J. and Tratnyek, P.G.: Reductive dehalogenation of chlorinated methanes by iron metal. Environ. Sci. Technol. 28, 2045 (1994).CrossRefGoogle ScholarPubMed
21.Gash, A.E., Tillotson, T.M., Satcher, J.H., Poco, J.F., Hrubesh, L.W. and Simpson, R.L.: Use of epoxides in the sol-gel synthesis of porous iron(III) oxide monoliths from Fe(III) salts. Chem. Mater. 13, 999 (2001).CrossRefGoogle Scholar
22.Shchukin, D.G., Schattka, J.H., Antonietti, M. and Caruso, R.A.: Photocatalytic properties of porous metal oxide networks formed by nanoparticle infiltration in a polymer gel template. J. Phys. Chem. B 107, 952 (2003).CrossRefGoogle Scholar
23.Caruso, R.A. and Schattka, J.H.: Cellulose acetate templates for porous inorganic network fabrication. Adv. Mater. 12, 1921 (2000).Google Scholar
24.Kresge, C.T., Leonowiez, M.E., Roth, W.J., Vartuli, J.C. and Beck, J.S.: Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359, 710 (1992).Google Scholar
25.Johnson, S.A., Ollivier, P.J. and Mallouk, T.E.: Ordered mesoporous polymers of tunable pore size from colloidal silica templates. Science 283, 963 (1999).CrossRefGoogle ScholarPubMed
26.Velev, O.D., Jede, T.A., Lobo, R.F. and Lenhoff, A.M.: Porous silica via colloidal crystallization. Nature 389, 447 (1997).Google Scholar
27.Park, S.H. and Xia, H.: Macroporous membranes with highly ordered and three-dimensionally interconnected spherical pores. Adv. Mater. 10, 1045 (1998).Google Scholar
28.Jiang, P., Cizeron, J., Bertone, J.F. and Colvin, V.L.: Preparation of macroporous metal films from colloidal crystals. J. Am. Chem. Soc. 121, 7957 (1999).CrossRefGoogle Scholar
29.Ding, Y. and Erlebacher, J.: Nanoporous metals with controlled multimodal pore-size distribution. J. Am. Chem. Soc. 125, 7772 (2003).Google Scholar
30.Kulinowski, K.M., Jiang, P., Vaswani, H. and Colvin, V.L.: Porous metals from colloidal templates. Adv. Mater. 12, 833 (2000).Google Scholar
31.Velev, O.D., Tessier, P.M., Lenhoff, A.M. and Kaler, E.W.: Materials: A class of porous metallic nanostructures. Nature 401, 548 (1999).CrossRefGoogle Scholar
32.Yan, H., Nalnford, C.F., Holland, B.T., Parent, M., Smyrl, W.H. and Stein, A.: A chemical synthesis of periodic macroporous NiO and metallic Ni. Adv. Mater. 11, 1003 (1999).Google Scholar
33.Harrison, R.G., Fox, O.D., Meng, M.O., Dalley, N.K. and Barbous, L.J.: Cation control of pore and channel size in cage-based metal-organic porous materials. Inorg. Chem. 41, 838 (2002).Google Scholar
34.Breulmann, M., Davis, S.A., Mann, S., Hentze, H. and Antonietti, M.: Polymer-gel templating of porous inorganic macro-structures using nanoparticle building blocks. Adv. Mater. 12, 502 (2000).Google Scholar
35.Zhang, W.X., Wang, C. and Lien, H.: Treatment of chlorinated organic contaminants with nanoscale bimetallic particles. Catal. Today 40, 387 (1998).Google Scholar
36.Zhang, W.X.: Nanoscale iron particles for environmental remediation: An overview. J. Nanopart. Res. 5, 323 (2003).Google Scholar
37.Ponder, S.M., Darab, J.G. and Mallouk, T.E.: Remediation of Cr(VI) and Pb(II) aqueous solutions using supported, nanoscale zero-valent iron. Environ. Sci. Technol. 34, 2564 (2000).Google Scholar
38.Kroschwitz, J. and Howe-Grant, M., Encyclopedia of Chemical Technology, 4th ed. (Wiley & Sons, New York, 1993).Google Scholar
39.Agency, U.S. Environmental Protection: Integrated Risk Information System (IRIS) (Environmental Criteria and Assessment Office, Cincinnati, OH, 1992).Google Scholar
40.Stumm, W. and Morgan, J.J.: Aquatic Chemistry, 3rd ed. (Wiley & Sons, New York, 1996).Google Scholar
41.Alowitz, M.J. and Scherer, M.M.: Kinetics of nitrate, nitrite, and Cr(VI) reduction by iron metal. Environ. Sci. Technol. 36, 299 (2002).Google Scholar
42.Hunger, K.: Industry Dyes: Chemistry, Properties, Applications (Wiley-VCH, Weinheim, Germany, 2003).Google Scholar
43.Cao, J., Wei, L., Huang, Q., Wang, L. and Han, S.: Reducing degradation of azo dye by zero-valent iron in aqueous solution. Chemosphere 38, 565 (1999).CrossRefGoogle ScholarPubMed
44.Namand, S. and Tratnyek, P.G.: Reduction of azo dyes with zero-valent iron. Water Res. 34, 1837 (2000).Google Scholar