Solid-liquid interfacial reaction of Zn ions on the surface of amorphous aluminosilicates with various Al/Si ratios |
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| Authors: | Akane Miyazaki Ioan Balint |
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| Institution: | 1 Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
2 Institute of Physical Chemistry, Romanian Academy, Spl. Independentei 202, 77208 Bucharest, Romania |
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| Abstract: | The adsorption behavior of Zn2+ ions onto the surface of amorphous aluminosilicates was studied using both potentiometric and spectroscopic methods (XANES: X-ray Absorption Near-Edge Structure). The aluminosilicates were prepared with different Al/Si ratios in order to compare the reactivities of surface aluminol and silanol groups toward Zn2+ ions. Potentiometric experiments were performed by maintaining the reacting suspensions at constant pH, ionic strength, and solid concentration, while Zn concentration was increased by stepwise addition. Our results showed that the surface aluminol and silanol groups possess significantly different reactivities toward Zn2+ ions. The reaction of Zn2+ ions with aluminol groups occurs through three processes: (i) surface complexation, (ii) dissolution, and (iii) re-sorption. A stoichiometric relationship was confirmed for the surface complexation between the aluminol groups and Zn2+ ions: two moles of H+ ions were released for one mole of Zn2+ ion adsorption. Following the surface complexation process, measurable amounts of zinc and aluminum ions were found to be mobilized from the surface of the solid to the liquid phase; subsequently, these ions precipitated on the solid surface, and possibly formed a co-precipitate with the hydrotalcite-type structure. On the other hand, a stoichiometric relationship was not obtained for the sorption of Zn2+ ions on silanol groups, and therefore, it was concluded that Zn2+ ions are retained on the surface of amorphous aluminosilicates by two different reactions. One reaction involves the surface complexation between Zn2+ ions and surface aluminol groups, which proceeds rapidly. The other reaction is the slow retention of Zn2+ ions onto silanol and/or aluminol groups, which could be the surface precipitation of Zn(OH)2 or the co-precipitation of Zn2+-Al3+ hydroxides. It can be suggested that the total sorption behavior of Zn2+ ions on amorphous aluminosilicates with different Al/Si ratios can be represented as the sum of the individual reactions of Zn2+ ions toward the aluminol and silanol groups. The potentiometric results were confirmed by XANES data. It was clearly evident that only the aluminol groups were responsible for surface complexation of Zn2+ ions. An equilibrium constant was calculated for this reaction. |
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