The layered double hydroxides (LDHs) Zn2Al(OH)6Cl·nH2O, Zn2Cr(OH)6Cl·nH2O, and Cu2Cr(OH)6Cl·nH2O have been shown to undergo staged intercalation reactions with succinate and tartrate anions. Monitoring the process in situ using energy-dispersive X-ray diffraction reveals the formation of second-stage intermediates caused by the filling of every second layer. Depending on the nature of the organic anion, the Bragg peaks of the second-stage intermediates and the fully organic exchanged materials emerge in two distinct sequences indicating two exchange pathways. For tartrate exchange, the fully exchanged material is not observed until the intermediate has gone through its maximum and the chloride precursor has disappeared completely, while for succinate exchange, the final state of intercalation and the second-stage intermediate simultaneously appear. Similar staging has previously been reported only for LiAl2(OH)6Cl·2H2O. These results demonstrate that staging in the intercalation of LDH does not involve a structural order of the host and cannot be explained by a tactoid mechanism.

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Molecular dynamics simulations of the ZnAl layered double hydroxide containing interlayer chloride anions have been performed in the NpT and Np(zz)T statistical ensembles for metal Zn/Al ratios of 2 and 3. We have monitored the interlayer spacing as a function of the number of intercalated water molecules for each statistical ensemble. We have studied how these profiles are affected by the method of calculation of the charges of the hydroxide layer atoms. Diffusion coefficients of the interlayer water molecules have been calculated for different Zn/Al ratios. The calculation of the chemical potential of the interlayer water molecules has been carried out for three amounts of interlayer water molecules. The calculation showed a qualitative agreement with the bulk water chemical potential within a range of interlayer water molecule contents.

The present study aims at investigating the structural and dynamics properties of intercalated tartrate and succinate anions in Zn 2 Al layered double hydroxides (LDHs). The comparison between these two anions allows the estimation of the impact of the presence of hydroxyl groups in tartrate on the dynamics, orientational, and rotational behaviors of the species in the interlayer domain. A variety of experimental techniques (X-ray diffraction, 1 H-13 C MAS NMR variable contact time, proton conductivity, microcalorimetry) is used in association with molecular dynamics (MD) simulations. A specific behavior is then established for the tartrate in terms of rotation around the backbone, diffusion, and organization of the water molecules in the interlayer domain. The difference in the enthalpies of exchange between the two LDHs is calculated from MD simulations and compared to that obtained by microcalorimetry experiments. This energy calculation evidences for the existence of anion-anion interactions that are more favorable for tartrate than for succinate. The combination of experimental and theoretical methods performs very well for the structural, energetic, and dynamics characterization of the interlayer species.