Sorption of gold by naked and thiol-capped magnetite nanoparticles: An XPS approach

Iron oxide nanoparticles are promising materials for many technological and environmental applications due to their versatile functionalization and magnetic properties that allow a facile remote control, separation and analyte recovery. In this contribution, the results of gold(III) sorption by naked and DMSA-capped (DMSA = m-2,3,dimercapto succinic acid) magnetite nanoparticles are discussed. Magnetite nanoparticles of 8 nm diameter were first synthesized by thermal decomposition of iron(III) oleate followed by a ligand exchange reaction to substitute oleic acid (OA) molecules by DMSA. Such systems of coated magnetite nanoparticles were characterized with Fourier transform infrared (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and magnetic measurements. FT-IR spectroscopy suggests that in Fe₃O ₄@DMSA the organic coating is not homogeneous and it interacts with surface iron cations either through the carboxylate groups (by forming bridging bidentate complexes) or through disulfide bonds after oxidation of thiol groups. The magnetic measurements show that the nanoparticles are in the superparamagnetic range at room temperature despite the presence of dipolar interactions. The gold(III) adsorption isotherms for both bare Fe ₃O₄ and Fe₃O₄@DMSA nanoparticles were fitted with the Langmuir and Freundlich models. The better fit for the second model suggests the heterogeneous nature of the surface and the multilayer nature of gold adsorption. XPS spectra reveal that the adsorption of Au(III) ions comprises mostly its reduction to Au⁰ by disulfide groups, although there is a fraction of these gold ions that is reduced directly onto the bare surface of the iron oxide leading to Fe(II) oxidation. According to the recorded optical absorption spectra, gold clusters of metallic character are also formed at the nanoparticle surface, a fraction of them forming subnanometer aggregates. The magnetic recovery of gold by this nanosystem could be extendable to other heavy metals.