Ambient-Temperature Synthesis, Evolution, and Characterization of Cobalt-Aluminum Hydrotalcite-Like Solids

Hillary A. Thompson1, †, George A. Parks1 and Gordon E. Brown Jr.1, 2
1 Department of Geological and Environmental Sciences, Stanford University, Stanford, California 94305-2115, USA
2 Stanford Synchrotron Radiation Laboratory, Stanford, California 94309, USA
Present address: Los Alamos National Laboratory, MS D469, Los Alamos, New Mexico 87545, USA.

Abstract: Double hydroxide solids precipitated homogeneously from three laboratory-synthesized aqueous solutions that simulated mildly contaminated surface or groundwater. Over a limited pH range, precipitates formed rapidly from dissolved ions, and more slowly by incorporating ions dissolving from other solids, including highly soluble aluminous solids. The precipitates were characterized by size and shape via transmission electron microscopy (TEM), by composition via inductively coupled plasma-mass spectrometry (ICP-MS) of mother solutions and analytical electron microscopy (AEM) of precipitates, and by structure via powder X-ray diffraction (XRD), TEM, and extended X-ray absorption fine structure (EXAFS) spectroscopy. They were identified as nanocrystalline cobalt hydrotalcite (CoHT) of the form [Co(II) 1−xAl(III)x(OH)2]x+(An−x/nmH2O, with x = 0.17–0.25, A = CO32−, NO3, or H3SiO4, n = anion charge and m undetermined. Complete solid solution may exist at the macroscopic level for the range of stoichiometries reported, but clustering of Co atoms within hydroxide layers indicates a degree of immiscibility at the molecular scale. Composition evolved toward the Co-rich endmember with time for at least one precipitate. The small layer charge in the x = 0.17 precipitate caused anionic interlayers to be incomplete, producing interstratification of hydrotalcite and brucite-like layers. Solubility products estimated from solution measurements for the observed final CoHT stoichiometries suggest that CoHT is less soluble than the inactive forms of Co(OH)2 and CoCO3 near neutral pH. Low solubility and rapid formation suggest that CoHT solids may be important sinks for Co in contact with near neutral pH waters. Because hydrotalcite can incorporate a range of transition metals, precipitation of hydrotalcite may be similarly effective for removing other trace metals from natural waters.

Key Words: Anionic Clay • Cation Ordering • Coprecipitation • EXAFS • Hydrotalcite • ICP-MS • Solubility Product • TEM • Metal Contamination • Solid Solution • Interstratification

Clays and Clay Minerals; August 1999 v. 47; no. 4; p. 425-438; DOI: 10.1346/CCMN.1999.0470405
© 1999, The Clay Minerals Society
Clay Minerals Society (www.clays.org)