Characterization of Chemisorbed Species and Active Adsorption Sites in Mg–Al Mixed Metal Oxides for High-Temperature CO₂ Capture

Mg-Al mixed metal oxides (MMOs), derived from the decomposition of layered double hydroxides (LDHs), have been purposed as adsorbents for CO₂ capture of industrial plant emissions. To aid in the design and optimization of these materials for CO₂ capture at 200 °C, we have used a combination of solid-state nuclear magnetic resonance (ssNMR) and density functional theory (DFT) to characterize the CO₂ gas sorption products and determine the various sorption sites in Mg-Al MMOs. A comparison of the DFT cluster calculations with the observed ¹³C chemical shifts of the chemisorbed products indicates that mono- and bidentate carbonates are formed at the Mg-O sites with adjacent Al substitution of an Mg atom, while the bicarbonates are formed at Mg-OH sites without adjacent Al substitution. Quantitative ¹³C NMR shows an increase in the relative amount of strongly basic sites, where the monodentate carbonate product is formed, with increasing Al/Mg molar ratios in the MMOs. This detailed understanding of the various basic Mg-O sites presented in MMOs and the formation of the carbonate, bidentate carbonate, and bicarbonate chemisorbed species yields new insights into the mechanism of CO₂ adsorption at 200 °C, which can further aid in the design and capture capacity optimization of the materials.