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Modified Clays for the Adsorption of Environmental Toxicants: Binding of Chlorophenols to Pillared, Delaminated, and Hydroxy-Interlayered Smectites

Published online by Cambridge University Press:  02 April 2024

Richard C. Zielke  and
Thomas J. Pinnavaia
Richard C. Zielke
Affiliation:
Department of Chemistry and Center for Fundamental Materials Research, Michigan State University, East Lansing, Michigan 48824
Thomas J. Pinnavaia
Affiliation:
Department of Chemistry and Center for Fundamental Materials Research, Michigan State University, East Lansing, Michigan 48824
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Abstract

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Due to their unique polarity, pore-size distribution, and high surface areas, pillared and delaminated clays are potentially useful materials for the adsorption of environmental toxicants. To determine their properties for adsorption of chlorinated phenols, alumina-pillared montmorillonite (APM), chromia-pillared montmorillonite (CPM), and alumina-delaminated Laponite (ADL) were reacted with aqueous pentachlorophenol (PCP) solutions in batch equilibrium experiments. An hydroxy-Al Laponite (HAL) in which the Na+ exchange ions were replaced by ions of the type Al13O4(OH)(24+x)(H2O)(12-x)(7-x)+ was included in the study. With ADL as the adsorbent, the extent of PCP adsorption increased with decreasing pH, and then became constant at pH ≤ pKa. Thus, the neutral phenol was preferred over the phenolate form. Binding of neutral PCP at pH 4.7 to all adsorbents never reached saturation values, and the loadings achieved were limited by the water solubility of the adsorbate. Among the pillared and delaminated clays investigated, ADL exhibited the largest capacity for physical adsorption of PCP at pH 4.7. Differences in the PCP binding capacities for APM, CPM, and ADL suggested that adsorption was dependent on the pore structure and surface composition of the modified clay adsorbent, not on surface area alone. HAL exhibited quantitative uptake of PCP at the 8 µmole/g level, indicating that a chemi-sorption mechanism may operate for PCP binding to this adsorbent. Adsorption of 3-chlorophenol, 3,5-dichlorophenol, and 3,4,5-trichlorophenol by ADL at pH 7.4 increased as the degree of hydrophobicity and chlorination of the phenol increased; hence, the binding capacity was not limited by the molecular size of the adsorbate. In contrast to the adsorption properties observed for pillared, delaminated, and hydroxy-interlayered clays, Na+-montmorillonite and Na+-Laponite did not adsorb PCP from aqueous solution.

Keywords

AdsorptionChlorophenolDelaminated smectiteHydroxy-AlLaponitePillared smectiteSmectiteToxicants
Type
Research Article
Information
Clays and Clay Minerals , Volume 36 , Issue 5 , October 1988 , pp. 403 - 408
Copyright
Copyright © 1988, The Clay Minerals Society

References

Adams, J. M., 1987 Synthetic organic chemistry using pillared, cation-exchanged and acid-treated montmorillonite catalysts. A review Appl. Clay Sci. 2 309 – 342.CrossRefGoogle Scholar
Ballantine, J. A. and Setton, R., 1986 The reactions in clays and pillared clays Chemical Reactions in Organic and Inorganic Constrained Systems Dordrecht NATO ASI Series C 165, Reidel 197 – 212.CrossRefGoogle Scholar
Bowers, A. R. and Huang, C. P., 1985 Adsorption characteristics of polyacetic amino acids onto hydrous γ-Al2O3 J. Colloid Inter. Sci. 105 197 – 215.CrossRefGoogle Scholar
Boyd, S. A., Mikesell, M. and Sawhney, B. L., 1988 Reactions of chlorophenols in soils Reactions and Movement of Organic Chemicals in Soils Wisconsin Soil Sci. Soc. Amer. Spec. Pub., Madison.Google Scholar
Boyd, S. A., Shaobai, S., Lee, J.-F. and Mortland, M. M., 1988 Pentachlorophenol sorption by organo-clays Clays & Clay Minerals 36 125 – 130.CrossRefGoogle Scholar
Chapman, P. M., Romberg, G. P. and Vigers, G. A., 1982 Design of monitoring studies for priority pollutants J. Water Pollution Control Federation 54 292 – 297.Google Scholar
Chiou, C. T., Peters, L. J. and Freed, V. H., 1979 A physical concept of soil-water equilibria for nonionic organic compounds Science 213 684 – 685.CrossRefGoogle Scholar
Chiou, C. T., Porter, P. E. and Schmedding, D. W., 1983 Partition equilibria of non-ionic organic compounds between soil organic matter and water Environ. Sci. Technol. 17 227 – 231.CrossRefGoogle Scholar
Fenn, D. B., Mortland, M. M. and Pinnavaia, T. J., 1973 The chemisorption of anisole on Cu(II) hectorite Clays & Clay Minerals 21 315 – 322.CrossRefGoogle Scholar
Flaig, W., Beutelspacher, H., Reitz, E. and Gieseking, J. E., 1975 Chemical composition and physical properties of humic substances Soil Components, Vol. 1, Organic Components New York Springer-Verlag 1 – 211.Google Scholar
Kummert, R. and Stumm, W., 1980 The surface complexation of organic acids on hydrous γ-Al2O3 J. Colloid Inter. Sci. 75 373 – 385.CrossRefGoogle Scholar
Kuwahara, M., Shindo, N. and Munakata, K., 1970 The photochemical reaction of pentachlorophenol J. Agric. Chem. Soc. Jpn. 44 169 – 174.Google Scholar
Landau, S. D., 1984 Physical and catalytic properties of hydroxy-metal interlayered smectite minerals Michigan Michigan State University, East Lansing 38 – 40.Google Scholar
Larson, R. A. and Hufnal, J. M., 1980 Oxidative polymerization of dissolved phenols by soluble and insoluble inorganic species Limnol. Oceanogr. 25 505 – 512.CrossRefGoogle Scholar
Martin, J. P. and Haider, K., 1971 Microbial activity in relation to soil humus formation Soil Sci. 111 54 – 63.CrossRefGoogle Scholar
McBride, M. B., Pinnavaia, T. J. and Mortland, M. M., 1977 Adsorption of aromatic molecules by clays in aqueous suspension Adv. Environ. Sci. Technol. 8 145 – 154.Google Scholar
Mortland, M. M., Shaobai, S. and Boyd, S. A., 1986 Clayorganic complexes as adsorbents for phenol and chlorophenols Clays & Clay Minerals 34 581 – 585.CrossRefGoogle Scholar
Occelli, M. L., Hsu, J. T. and Gayla, L. G., 1985 Propylene oligomerization with pillared clays J. Molec. Catal. 33 371 – 389.CrossRefGoogle Scholar
Pinnavaia, T. J., 1983 Intercalated clay catalysts Science 220 365 – 371.CrossRefGoogle ScholarPubMed
Pinnavaia, T. J., Landau, S. D., Tzou, M.-S. and Johnson, I. D., 1985 Layer cross-linking in pillared clays J. Amer. Chem. Soc. 107 7222 – 7224.CrossRefGoogle Scholar
Pinnavaia, T. J., Tzou, M.-S. Landau, S. D. and Raythatha, R. H., 1984 On the pillaring and delamination of smectite clay catalysts by polyoxo cations of aluminum J. Molec. Catal. 27 195 – 212.CrossRefGoogle Scholar
Plee, D., Borg, F., Gatineau, L. and Fripiat, J. J., 1985 High resolution solid state 27Al and 29Si nuclear magnetic resonance study of pillared clays J. Amer. Chem. Soc. 107 2362 – 2369.CrossRefGoogle Scholar
Poncelet, G., Shultz, A. and Setton, R., 1986 Pillared montmorillonite and beidellite. Acidity and catalytic properties Chemical Reactions in Organic and Inorganic Constrained Systems Dordrecht NATO ASI Series C165, Reidel 165 – 178.CrossRefGoogle Scholar
Rightor, E. G. and Pinnavaia, T. J., 1987 STEM studies of ruthenium dispersed on a pillared clay Fisher-Tropsch catalyst Ultramicroscopy 22 159 – 173.CrossRefGoogle Scholar
Sawhney, B. L., 1985 Vapor-phase sorption and polymerization of phenols by smectite in air and nitrogen Clays & Clay Minerals 33 123 – 127.CrossRefGoogle Scholar
Shindo, H. and Huang, P. M., 1985 The catalytic power of inorganic components in the abiotic synthesis of hydroquinone-derived humic polymers Appl. Clay Miner. 1 71 – 85.CrossRefGoogle Scholar
Stevenson, F. J., 1982 Humus Chemistry-Genesis, Composition, Reactions New York Wiley 205 – 215.Google Scholar
Suib, S. L., Tanquay, J. F. and Occelli, M. L., 1986 Comparison of the photochemical and photophysical properties of clays, pillared clays, and zeolites J. Amer. Chem. Soc. 108 6972 – 6977.CrossRefGoogle Scholar
Tennakoon, P. T. B. Jones, W. and Thomas, J. M., 1986 Structural aspects of metal-oxide pillared sheet silicates J. Chem. Soc. Farad. Trans. 82 3081 – 3095.CrossRefGoogle Scholar
Thompson, T. D. and Moll, W. F., 1973 Oxidative power of smectites measured by hydroquinone Clays & Clay Minerals 21 337 – 350.CrossRefGoogle Scholar
Wang, T. S. C. Li, S. W. and Femg, Y. L., 1978 Catalytic polymerization of phenolic compounds by clay minerals Soil Sci. 126 15 – 21.CrossRefGoogle Scholar