Quantitative analyses of shape-selective intercalation of isomeric mixtures of muconates into [LiAl_2(OH)_6]Cl(centre dot)yH_2O layered double hydroxide

摘要

Quantitative investigastion of the shape selectivity for the competitive intercalation reaction of isomeric mixtures in the interlayer of LDH was achieved by analyzing the solid phases synthesized by the reaction of [LiAl_2(OH)_6]Cl(centre dot)yH_2O with various compositional mixtures of (E,E)- and (Z,Z)-muconates. The apparent partition constant K' for the anion-exchange reaction between (E,E)-and (Z,Z)-muconates was quite dependent on the mole fraction of muconates in solution. The only single phase saturated with [LiAl_2(OH)_6]_2(E,E)-C_6H_4O_4)(centre dot)zH_2O could be obtained in the range of the initial mole fraction of (E,E)-muconate larger than 0.6 in the starting solution, while mixed phases intercalated with (E,E)- and (Z,Z)-muconates could be obtained at lower mole fractions of (E,E)-muconate. The shape selectivity for the competitive reaction of two muconates on the [LiAl_2(OH)_6]~+ lattice could be ascribed to thermodynamic processes, and the conditions under which that pure (E,E)-muconate was efficiently separated from isomeric mixtures of two muconates were successfully evaluated.