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Influence of Gibbsite Surface Area and Citrate on Ni Sorption Mechanisms at pH 7.5

Published online by Cambridge University Press:  01 January 2024

Noriko U. Yamaguchi ,
Andreas C. Scheinost  and
Donald L. Sparks
Noriko U. Yamaguchi*
Affiliation:
Department of Quantum Engineering and Systems Science, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo Bunkyo-ku Tokyo, 113-8656, Japan
Andreas C. Scheinost
Affiliation:
Institute of Terrestrial Ecology, ETHZ, 8952 Schlieren, Switzerland
Donald L. Sparks
Affiliation:
Department of Plant and Soil Sciences, University of Delaware, Newark, DE 19717-1303, USA
*
*E-mail address of corresponding author: n-yamaguchi@q.t.u-tokyo.ac.jp
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Abstract

We investigated the sorption of Ni to gibbsite of two different surface areas at pH 7.5, in the presence and absence of citrate, over a time period of 180 days. Extended X-ray absorption fine-structure spectroscopy was employed to elucidate the sorption mechanisms at the molecular level. In agreement with former results, Ni-Al layered double hydroxide (LDH) formed in the presence of gibbsite of low surface area. However, gibbsite of high surface area suppressed the formation of the surface precipitate. Instead, two Al atoms neighboring Ni at distances of 2.95–2.98 Å indicated formation of an inner-sphere sorption complex, where each NiO6-octahedron shares edges with two AlO6-octahedra. Focused multiple scattering arising from Al atoms at a distance of 6 Å suggest that sorbed Ni(OH)2(OH2)4 monomers epitaxially extend the hexagonal arrangement of Al atoms in gibbsite. Only after 30 days or more was a small amount of LDH formed. The presence of citrate prevented the formation of LDH, while maintaining the formation of inner-sphere sorption complexes.

Keywords

CitrateEXAFSGibbsiteLayered Double HydroxideNiSorptionSurface AreaSurface Precipitate
Type
Research Article
Information
Clays and Clay Minerals , Volume 50 , Issue 6 , December 2002 , pp. 784 - 790
Copyright
Copyright © 2002, The Clay Minerals Society

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