Deterioration of anion-adsorption abilities of layered double hydroxides synthesized in agarose gel

With the goal of improving solid-liquid separability in wastewater treatment, Mg-Al layered double hydroxides (LDH) were synthesized in agarose gel, and the resulting LDH-containing hybrid hydrogels were dried. The anion-adsorption abilities of the dried hydrogels were compared with those of LDH synthesized by means of a conventional constant-pH coprecipitation method at low supersaturation. A surprising result was found: the adsorption abilities of the dried hybrid hydrogels decreased with storage time, whereas the adsorption abilities of the LDH synthesized by the conventional method remained essentially constant. Further investigation revealed that the adsorption abilities of LDH synthesized by rapid mixing of aqueous Mg-Al and aqueous NaOH at high supersaturation (i.e., a method similar to that used to prepare the hybrid hydrogel) also decreased over time. Therefore, only LDH synthesized by coprecipitation at high supersaturation showed deterioration during storage time in anion-adsorption abilities. Observed results that accompanied the deterioration suggest that the decrease was due to the formation of pockets of mutually adjacent Al-occupied cation sites in the metal hydroxide layers of the Mg-Al LDH as a result of rapid mixing of the starting solutions. The presence of mutually adjacent Al-occupied sites is thought to be in instability due to mutual repulsion. This instability may have led to gradual decomposition of hydroxide moieties containing mutually adjacent Al-occupied sites together with interlayer anions of OH- and Cl- to form aluminum hydroxide or basic aluminum chloride, as well as to separation of nearby Mg(OH)(2) moieties from LDH structure.