Synthesis of Highly Reactive Subnano-sized Zero-valent Iron Using Smectite Clay Templates

Overview

Journal Environ Sci Technol

Publisher American Chemical Society

Specialty Environmental Health

Date 2010 May 8

PMID 20446730

Citations 10

Authors

Cheng Gu

Hanzhong Jia

Hui Li

Brian J Teppen

Stephen A Boyd

Affiliations

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Abstract

A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH(4), resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of approximately 5 A. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the X-ray diffraction (XRD) results since the diameter of elemental Fe is 2.5 A. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene/non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnanoscale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, for example, as components of constructed reactive domains such as reactive caps for contaminated sediments.

Citing Articles

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References

Danganan C, Ye R, Daubaras D, Xun L, Chakrabarty A . Nucleotide sequence and functional analysis of the genes encoding 2,4,5-trichlorophenoxyacetic acid oxygenase in Pseudomonas cepacia AC1100. Appl Environ Microbiol. 1994; 60(11):4100-6. PMC: 201942. DOI: 10.1128/aem.60.11.4100-4106.1994. View

Quinn J, Geiger C, Clausen C, Brooks K, Coon C, OHara S . Field demonstration of DNAPL dehalogenation using emulsified zero-valent iron. Environ Sci Technol. 2005; 39(5):1309-18. DOI: 10.1021/es0490018. View

Aggarwal V, Li H, Boyd S, Teppen B . Enhanced sorption of trichloroethene by smectite clay exchanged with Cs+. Environ Sci Technol. 2006; 40(3):894-9. DOI: 10.1021/es0500411. View

Zhu B, Lim T, Feng J . Reductive dechlorination of 1,2,4-trichlorobenzene with palladized nanoscale Fe(zero-valent) particles supported on chitosan and silica. Chemosphere. 2006; 65(7):1137-45. DOI: 10.1016/j.chemosphere.2006.04.012. View

Neumann A, Hofstetter T, Lussi M, Cirpka O, Petit S, Schwarzenbach R . Assessing the redox reactivity of structural iron in smectites using nitroaromatic compounds as kinetic probes. Environ Sci Technol. 2008; 42(22):8381-7. DOI: 10.1021/es801840x. View

Zhou P, Yan H, Gu B . Competitive complexation of metal ions with humic substances. Chemosphere. 2005; 58(10):1327-37. DOI: 10.1016/j.chemosphere.2004.10.017. View

Hofstetter T, Neumann A, Schwarzenbach R . Reduction of nitroaromatic compounds by Fe(II) species associated with iron-rich smectites. Environ Sci Technol. 2006; 40(1):235-42. DOI: 10.1021/es0515147. View

Boyd S, Sheng G, Teppen B, Johnston C . Mechanisms for the adsorption of substituted nitrobenzenes by smectite clays. Environ Sci Technol. 2001; 35(21):4227-34. DOI: 10.1021/es010663w. View

Frost R, Xi Y, He H . Synthesis, characterization of palygorskite supported zero-valent iron and its application for methylene blue adsorption. J Colloid Interface Sci. 2009; 341(1):153-61. DOI: 10.1016/j.jcis.2009.09.027. View

10.

Chen C, Lei P, Ji H, Ma W, Zhao J, Hidaka H . Photocatalysis by titanium dioxide and polyoxometalate/TiO2 cocatalysts. Intermediates and mechanistic study. Environ Sci Technol. 2004; 38(1):329-37. DOI: 10.1021/es034384f. View

11.

Huang Q, Shi X, Pinto R, Petersen E, Weber Jr W . Tunable synthesis and immobilization of zero-valent iron nanoparticles for environmental applications. Environ Sci Technol. 2009; 42(23):8884-9. DOI: 10.1021/es8015588. View

12.

Elsner M, Schwarzenbach R, Haderlein S . Reactivity of Fe(II)-bearing minerals toward reductive transformation of organic contaminants. Environ Sci Technol. 2004; 38(3):799-807. DOI: 10.1021/es0345569. View

13.

ELLIOTT D, Zhang W . Field assessment of nanoscale bimetallic particles for groundwater treatment. Environ Sci Technol. 2002; 35(24):4922-6. DOI: 10.1021/es0108584. View

14.

Choe S, Lee S, Chang Y, Hwang K, Khim J . Rapid reductive destruction of hazardous organic compounds by nanoscale Fe0. Chemosphere. 2000; 42(4):367-72. DOI: 10.1016/s0045-6535(00)00147-8. View

15.

Cundy A, Hopkinson L, Whitby R . Use of iron-based technologies in contaminated land and groundwater remediation: a review. Sci Total Environ. 2008; 400(1-3):42-51. DOI: 10.1016/j.scitotenv.2008.07.002. View

16.

Johnston C, Sheng G, Teppen B, Boyd S, de Oliveira M . Spectroscopic study of dinitrophenol herbicide sorption on smectite. Environ Sci Technol. 2003; 36(23):5067-74. DOI: 10.1021/es025760j. View

17.

Hofstetter T, Schwarzenbach R, Haderlein S . Reactivity of Fe(II) species associated with clay minerals. Environ Sci Technol. 2003; 37(3):519-28. DOI: 10.1021/es025955r. View

18.

Liu C, Li H, Teppen B, Johnston C, Boyd S . Mechanisms associated with the high adsorption of dibenzo-p-dioxin from water by smectite clays. Environ Sci Technol. 2009; 43(8):2777-83. DOI: 10.1021/es802381z. View

19.

Klausen J, Troeber S, Haderlein S, Schwarzenbach R . Reduction of Substituted Nitrobenzenes by Fe(II) in Aqueous Mineral Suspensions. Environ Sci Technol. 2012; 29(9):2396-404. DOI: 10.1021/es00009a036. View

20.

Zhu B, Lim T . Catalytic reduction of chlorobenzenes with Pd/Fe nanoparticles: reactive sites, catalyst stability, particle aging, and regeneration. Environ Sci Technol. 2007; 41(21):7523-9. DOI: 10.1021/es0712625. View