Study on coordination structure of Re adsorbed on Mg–Al layered double hydroxide using X-ray absorption fine structure
Résumé
Porous materials of hydrotalcite-like layered double hydroxides (LDHs) have been used for removal of anionic contaminants from solution. However, local coordination structures of anions adsorbed on LDHs are not fully understood because of the lack of spectroscopic studies. In this study, we utilized X-ray absorption fine structure spectroscopy to clarify the coordination structure of Re in Mg–Al LDH as a surrogate of Tc. Adsorption experiments of ReO4− on calcined and uncalcined Mg–Al LDHs were conducted in aqueous solutions with different concentrations of NaCl, NaNO3, and Na2SO4. The tested calcined and uncalcined Mg–Al LDHs were characterized by chemical composition analysis, scanning electron microscopy (SEM), and BET surface area. Calcined Mg–Al LDH showed much higher adsorption than uncalcined one. The adsorption of ReO4− was reversible, and decreased with increasing concentration of competing anions like Cl−, NO3−, or SO42−. Rhenium LIII-edge X-ray absorption near edge structure suggested that neither redox reaction nor change of coordination structure occurred during intercalation of Re into Mg–Al LDH. Analysis of Re LIII-edge extended X-ray absorption fine structure indicated that ReO4− was adsorbed as an outer-sphere complex on Mg–Al LDH. The observed Re adsorption–desorption behavior, which was sensitive to the presence of competing anions, was consistent with the formation of outer sphere-complex.