Aldolization is a crucial carbon–carbon coupling reaction used in the conversion of biomass-derived platform molecules into valuable chemicals and fuels. In this work, we combine experiment and theory to explore the role thermal decomposition has in controlling the structure of alkali-free Mg-Al layered double hydroxides (LDHs) and their subsequent performance in the base-catalyzed aldol condensation of acetone, focusing on the constituent aldolization and dehydration steps. LDHs were synthesized via co-precipitation and subjected to calcination at temperatures up to 600 °C to produce mixed metal oxides of the form Mg3AlOz which were further examined by SEM, N2 physisorption, XRD, and CO2-TPD. Aldolization and dehydration behaviors were examined in a batch reactor and fit with kinetic models to capture the sensitivities of both reactions to calcination temperature. Additional experiments involving the selective blocking of base sites by CO2 poisoning and reversal at varying temperatures showed that both aldolization and dehydration are likely driven by the strongest base sites, yielding a site density (0.19 μmol m−2) in agreement with separate propionic acid titration studies. Density functional theory (DFT) simulations of Mg5Al2O8 surfaces were employed to gain microscopic insights into these materials, revealing the importance of Al substitution in creating cation vacancies which can drive aldol condensation through enolate intermediates stabilized in the oxyanion resonance form. High-coverage simulations of the surface show participation of the vacancy in both aldolization and dehydration, rationalizing the coupling of rate trends observed experimentally. Ultimately, this study provides new insights and approaches useful in the design of heterogeneous aldolization catalysts.
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