Comprehensive Analysis of the Chemical and Structural Transformations of Mg-Al-CO3 Layered Double Hydroxides with Different Mg/Al Ratios at Elevated Temperatures

Mg-Al layered double hydroxides (LDHs) with CO32- interlayer anions are promising CO2 adsorbents. Here, we analyzed the quantitative gas evolution behaviors of Mg-Al LDH particles with different Mg/Al ratios during the multistep chemical/structural transformations at elevated temperatures. The Mg/Al molar ratio strongly affects the behavior: the transformation changes from two apparent steps to three steps depending on the Mg/Al ratio. The transformation occurs in essentially the same way as that observed for large Mg-Al LDH crystals: (1) release of the interlayer water, (2) partial dehydroxylation of the hydroxyl layers followed by coordination of carbonate ions to the metals, and (3) collapse of the layered structure. We provide a molecular/atomic level picture of the structure in each step of the transformation by first-principles density functional theory (DFT) calculation. The structurally optimized model and reexamination of experimental data showed that step (1) results in a large decrease in the interlayer distance of the LDH from similar to 7.6 to similar to 6.7 & Aring; (a decrease of similar to 0.9 & Aring;) and the possible explanation is the waving of the metal hydroxide layers. This study provides a comprehensive understanding of the structural changes of LDHs with various Mg/Al ratios to resolve the various interpretations in the literature.

Automated summary

In this study, the gas evolution behaviors of Mg-Al layered double hydroxides (LDHs) during chemical/structural transformations at elevated temperatures were analyzed. The Mg/Al ratio was found to strongly affect the behavior, with the transformation changing from two steps to three steps depending on the ratio. First-principles density functional theory (DFT) calculation provided a molecular/atomic level picture of the structure in each step, offering a comprehensive understanding of the structural changes of LDHs with different Mg/Al ratios.