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Influence of Silicon and Phosphorus on Structural and Magnetic Properties of Synthetic Goethite and Related Oxides

Published online by Cambridge University Press:  02 April 2024

Thomas G. Quin ,
Gary J. Long ,
Christopher G. Benson ,
Stephen Mann  and
Robert J. P. Williams
Thomas G. Quin
Affiliation:
Inorganic Chemistry Laboratory and the Chemical Crystallography Laboratory, Oxford University, Oxford OX1 3QR, United Kingdom
Gary J. Long
Affiliation:
Department of Chemistry, University of Missouri-Rolla, Rolla, Missouri 65401, United Kingdom Department of Physics, University of Liverpool, Liverpool L69 3BX, United Kingdom
Christopher G. Benson
Affiliation:
Department of Chemistry, University of Missouri-Rolla, Rolla, Missouri 65401, United Kingdom Department of Physics, University of Liverpool, Liverpool L69 3BX, United Kingdom
Stephen Mann
Affiliation:
School of Chemistry, University of Bath, Bath BA2 7AY, United Kingdom
Robert J. P. Williams
Affiliation:
Inorganic Chemistry Laboratory and the Chemical Crystallography Laboratory, Oxford University, Oxford OX1 3QR, United Kingdom
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Abstract

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A series of synthetic goethites containing varying amounts of Si and P dopants were characterized by X-ray powder diffraction, electron diffraction, microbeam electron diffraction, and Mössbauer spectroscopy. Very low level incorporation produced materials having structural and spectral properties similar to those of poorly crystalline synthetic or natural goethite. At higher incorporation levels, mixtures of noncrystalline materials were obtained which exhibited Mössbauer spectra typical of noncrystalline materials mixed with a superparamagnetic component. Microbeam electron diffraction indicated that these mixtures contained poorly crystalline goethite, poorly crystalline ferrihydrite, and a noncrystalline component. If the material was prepared with no aging of the alkaline Fe3+ solution before the addition of Na2HPO4 or Na2SiO3, materials were obtained containing little if any superparamagnetic component. If the alkaline Fe3+ solution was aged for 48 hr before the addition, goethite nuclei formed and apparently promoted the precipitation of a superparamagnetic phase. The Mössbauer-effect hyperfme parameters and the saturation internal-hyperfine field obtained at 4.2 K were typical of those of goethite; however, the Mössbauer spectra indicated that the ordering temperature, as reflected in the relaxation rate and/or the blocking temperature, decreased with increasing incorporation of Si and P. The complete loss of crystallinity indicates that Si and P did not substitute for Fe, but rather adsorbed on crystal-growth sites, thereby preventing uniform crystal growth.

Keywords

Electron diffractionFerrihydriteGoethiteMössbauer spectroscopyPhosphorusSiliconX-ray powder diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 36 , Issue 2 , April 1988 , pp. 165 - 175
Copyright
Copyright © 1988, The Clay Minerals Society

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