Active Site Ensembles Enabled C–C Coupling of CO₂ and CH₄ for Acetone Production

The production of acetone through ketonization of acetic acid is both energy intensive and environmentally detrimental, as it emits equimolecular CO2. Herein, a novel approach for acetone production from CO2 and CH4 was proposed through consecutive C–C coupling based on an extensive density functional theory computational study. To realize the consecutive C–C coupling, CeO2-based catalyst doped with Zn site ensemble was constructed. Direct coupling of CH3* with the acetate species, formed from C–C coupling of CO2 and stabilized CH3*, could be achieved to produce acetone. The results show that carbon chain growth is possible on the active site ensembles constructed on a CeO2-based catalyst. The coupling of the acetate species with the methyl moiety follows a nucleophilic addition mechanism and has apparent activation energies of 0.25 and 0.14 eV on Ovac (oxygen vacancy) and neutral surfaces, respectively. This process could potentially replace the traditional acetone production technology based on ketonization of acetic acid.