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Luminescence and ESR studies of relationships between O−-centres and structural iron in natural and synthetically hydrated kaolinites

Published online by Cambridge University Press:  09 July 2018

Lelia M. Coyne ,
Patricia M. Costanzo  and
B. K. G. Theng
Lelia M. Coyne
Affiliation:
Department of Chemistry, San Jose State University, Mail Stop 239-4, NASA-Ames Research Center, Moffett Field, CA 94035
Patricia M. Costanzo
Affiliation:
Department of Geology, University at Buffalo, State University of New York, 4240 Ridge Lea Road, Buffalo, NY 14226, USA
B. K. G. Theng
Affiliation:
NZ Soil Bureau, DSIR, Private Bag, Lower Hutt, New Zealand
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Abstract

Luminescence, induced by dehydration and by wetting with hydrazine and unsymmetrically substituted hydrazine, and related ESR spectra have been observed from several kaolinites, synthetically hydrated kaolinites, and metahalloysites. The amine-wetting luminescence results suggest that intercalation, not a chemiluminescence reaction, is the luminescence trigger. Correlation between dehydration-induced luminescence and g = 2 ESR signals associated with O−-centres in several natural halloysites, and concurrent diminution of the intensity of both these signal types as a function of aging in two 8.4 Å synthetically hydrated kaolinites, confirm a previously-reported relationship between the luminescence induced by dehydration and in the presence of O−-centres (holes, i.e., electron vacancies) in the tetrahedral sheet. Furthermore, the ESR spectra of the 8.4 Å hydrate showed a concurrent change in the line shape of the g = 4 signal from a shape usually associated with structural Fe in an ordered kaolinite, to a simpler one typically observed in more disordered kaolinite, halloysite, and montmorillonite. Either structural Fe centres and the O−-centres interact, or both are subject to factors previously associated with degree of order. The results question the long-term stability of the 8.4 Å hydrate, although XRD does not indicate interlayer collapse over this period. Complex inter-relationships are shown between intercalation, stored energy, structural Fe, and the degree of hydration which may be reflected in catalytic as well as spectroscopic properties of the clays.

Type
Research Article
Information
Clay Minerals , Volume 24 , Issue 4 , December 1989 , pp. 671 - 693
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1989

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References

Angel, B.R. & Hall, P.L. (1973) Electron-spin resonance studies of kaolins Proc. Int. Clay. Conf. Madrid, 47–60.Google Scholar
Angel, B.R., Jones, J.P.E. & Hall, P.L. (1974) Electron spin resonance studies of doped synthetic kaolinites I. Clay Miner., 10, 247–256.Google Scholar
Angel, B.R., Richards K. & Jones, R.P.E. (1976) The synthesis, morphology and general properties of kaolinites specifically doped with metallic ions and defects generated by irradiation. Proc. Int. Clay Conf. Mexico City,, 297–304.Google Scholar
Angel, B.R., Cuttler, A.H., Richards K. & Vincent, W.E. J. (1977) Synthetic kaolinites doped with Fe2+ and Fe3+ ions. Clays Clay Miner., 25, 381–383.Google Scholar
Angel, B.R. & Vincent, W.E.J. (1978) Electron spin resonance studies of iron oxides associated with the surface of kaolins. Clays Clay Miner., 26, 263–272.CrossRefGoogle Scholar
Back, R.A. (1984) The preparation, properties and reactions of diimide. Rev. Chem. Intermed., 5, 293–323.CrossRefGoogle Scholar
Bell, P.M., Mao, H.K. & Rossman, G.R. (1975) Absorption spectroscopy of ionic and molecular units in crystals and glasses. Pp. 16–20 in: Infrared and Raman Spectroscopy of Lunar and Terrestrial Materials(Karr Jr., C., editor). Academic Press, New York.Google Scholar
Brindley, G.W., Kao C-C., Harrison, J.L., Lipsicas, M. & Raythatha, R. (1986) Relation between structural disorder and other characteristics of kaolinites and dickites. Clays Clay Miner., 34, 239–249.CrossRefGoogle Scholar
Bube, R. (1960) Photoconductivity of Solids. Wiley, New York.Google Scholar
Chaikum, N. & Carr, R.M. (1987) Electron spin resonance studies of kaolinites. Clay Miner., 22, 287–296.Google Scholar
Churchman, G.J. & Theng, B.K.G. (1984) Interactions of halloysites with amides: mineralogical factors affecting complex formation. Clay Miner., 19, 161–175.Google Scholar
Costanzo, P.M., Clemency, C.V. & Giese, R.F. (1980) Low temperature synthesis of a 10 A hydrate of kaolinite using dimethylsulfoxide and ammonium fluoride. Clays Clay Miner., 28, 155–156.Google Scholar
Costanzo, P.M., Giese, R.F. Jr. & Clemency, C.V. (1984a) Synthesis of a 10 A hydrated kaolinite. Clays Clay Miner., 32, 29–35.CrossRefGoogle Scholar
Costanzo, P.M., Giese , R.F., Jr. & Lipsicas M. (1984b) Static and dynamic structure of water in hydrated kaolinites: Part I. The static structure. Clays Clay Miner., 32, 419–428.Google Scholar
Coyne, L.M., Lahav N. & Lawless, J.G. (1981a) Dehydration-induced luminescence in clay minerals. Nature, 292, 819–821.Google Scholar
Coyne, L.M., Lawless, J.G., Lahav, N., Sutton, S. & Sweeney, M. (1981b) Clays as prebiotic photocatalysts. Pp. 115–124 in: Origins of Life(Wolman, Y., editor). Reidel, Dordrecht.CrossRefGoogle Scholar
Coyne, L.M., Sweeney, M. & Hovatter, W. (1983) Luminescence induced by dehydration of kaolin - Association with electron spin active centers and with surface activity for dehydration-polymerization of glycine. J. Lumin., 28, 395–409.Google Scholar
Coyne, L.M., Pollock, G. & Kloepping, R. (1984) Room-temperature luminescence from kaolin induced by organic amines. Clays Clay Miner., 32, 58–66.CrossRefGoogle ScholarPubMed
Coyne, L.M. (1985) A possible energetic role of mineral surfaces in chemical evolution. Origins Life, 15, 161–206.CrossRefGoogle ScholarPubMed
Coyne, L.M. & Banin, A. (1986) Effect of adsorbed iron on thermoluminescence and electron spin resonance spectra of Ca-Fe-exchanged montmorillonite. Clays Clay Miner., 34, 645–650.Google Scholar
Cuttler, A.H. (1980) The behaviour of a synthetic 57Fe-doped kaolin: Mossbauer & electron paramagnetic resonance studies. Clay Miner., 15, 429–444.Google Scholar
Cuttler, A.H. (1981) Further studies of a ferrous iron-doped synthetic kaolin: Dosimetry of X-ray induced defects. Clay Miner., 16, 69–80.Google Scholar
Giese, R.F. & Constanzo, P.M. (1979) Synthesis of a monohydrate of kaolinite with ^001 = 8-4 A. Geol. Soc. Am.Abstr. 11, p. 432.Google Scholar
Giese, R.F. & Costanzo, P.M. (1986) Behaviour of water on the surface of kaolin minerals. Pp. 37–53 in: Geochemical Processes at Mineral Surfaces (Davis, J.A. & Hayes, K.F., editors). Am. Chem. Soc.Google Scholar
Hall, P.L. (1980) The application of electron spin resonance spectroscopy to studies of clay minerals: I. Isomorphous substitutions and external surface properties. Clay Miner., 15, 321–335.Google Scholar
Herbillon, A.J., Mestdagh, M.M., Vielvoye L. & Derouane, E.G. (1976) Iron in kaolinite with special reference to kaolinite from tropical soils. Clay Miner., 11, 201–219.Google Scholar
Jepson, B. (1988) Structural iron in kaolinites and in associated ancillary minerals. Pp. 467–529 in: Iron in Soil and Clay Minerals (Stucki, J.W., Goodman, B.A. & Schwertman, U., editors). Reidel, Dordrecht.CrossRefGoogle Scholar
Jones, J.P.E., Angel, B.R. & Hall, P.L. (1974) Electron spin resonance studies of doped synthetic kaolinite. II. Clay Miner., 10, 257–270.Google Scholar
Lahav, N., Coyne, L.M. & Lawless, J.G. (1982) Prolonged triboluminescence in clay minerals. Clays Clay Miner., 30, 73–75.CrossRefGoogle Scholar
Lahav, N., Coyne, L.M. & Lawless, J.G. (1985) Characterization of dehydration-induced luminescence of kaolinite. Clays Clay Miner., 33, 207–213.CrossRefGoogle Scholar
Meads, R.E. & Malden, P.J. (1975) Electron spin resonance in natural kaolinites containing Fe3+ and other transition metal ions. Clay Miner., 10, 313–345.Google Scholar
Mestdagh, M.M., Vielvoye, L. & Herbillon, A.J. (1980) Iron in kaolinite. II: The relationship between kaolinite crystallinity and iron content. Clay Miner., 15, 313–345.Google Scholar
Schmidt, E.W. (1984) Hydrazine and its Derivatives Preparation, Properties, Applications. Wiley, New York.Google Scholar
Siegel, F.R., Vaz, J.E. & Ronca, L.B. (1968) Thermoluminescence of clay minerals. Pp. 635-641 in: Thermoluminescence of Geological Materials. (McDougall, D.J., editor). Academic Press, London.Google Scholar
Singh, A. (1978) Introduction: Interconversion of singlet oxygen and related species. Photochem. Photobiol., 28, 429–433.Google Scholar
Solomon, D.H. (1968) Clay minerals as electron acceptors and donors in organic reactions. Clays Clay Miner., 16, 31–39.CrossRefGoogle Scholar
Solomon, D.H. & Hawthorne, D.G. (1983) Chemistry of Pigments and Fillers, p. 63. Wiley, New York. Google Scholar
Theng, B.K.G. (1982) Clay-activated organic reactions. Proc. Int. Clay Conf. Bologna-Pavia,, 197–238. Google Scholar
Thompson, J.G. (1986) Incomplete intercalation of kaolinite. 23rd Ann. Meet. Clay Miner. Soc. Jackson Mississippi. Abstract, p. 32.Google Scholar
Van Dyke, K. (1985) Bioluminescence and Chemiluminescence: Instruments and Application. Vols. I & 2. CRC Press, Boca Raton, FI.Google Scholar
Van Olphen, H. (1977) An Introduction to Clay Colloid Chemistry, 2nd Edition. Wiley-Interscience, New York.Google Scholar
Van Olphen, H. & Fripiat, J.J. (1979) Data Handbook for Clay Minerals and Other Non-Metallic Minerals. Pergamon Press, Oxford, England.Google Scholar