Chemical and Structural Transformations of <i>M</i>–Al–CO₃ Layered Double Hydroxides (<i>M</i> = Mg, Zn, or Co, <i>M</i>/Al = 2) at Elevated Temperatures: Quantitative Descriptions and Effect of Divalent Cations

Layered double hydroxides (LDHs) exhibit diverse chemical compositions and are being designed for promising applications such as CO₂ adsorbents. Although many researchers have analyzed CO₂ gas evolution and structural transformation behavior at elevated temperatures, there are still inconsistencies in results on the effect of different metal ions in LDHs. In this study, on the basis of atomic/molecular-level findings from our previous study on multistep structural/chemical transformation of Mg-Al LDHs, we analyzed the quantitative gas evolution behavior and structural transformations of <i>M</i>-Al-CO₃ LDHs with different divalent metal ions (<i>M</i> = Mg, Zn, or Co, <i>M</i>/Al = 2) at elevated temperatures. Our quantitative analysis revealed that all three LDH samples undergo the three-step chemical transformations: release of interlayer water, partial dehydroxylation of the hydroxyl layers, and complete dehydroxylation of layers and decomposition of interlayer CO₃^2-. However, the temperature range for each step differs, as do the structural transformations for each sample: the layered structure collapses in the first step for Zn-Al LDH and Co-Al LDH, and the third step for Mg-Al LDH. Our results provide for quantitative and concrete understanding of the effect of divalent metal ions in LDHs on thermal decomposition.