화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.134, No.45, 18804-18808, 2012
Solvent-Driven Reductive Activation of Carbon Dioxide by Gold Anions
Catalytic activation and electrochemical reduction. of CO2 for the formation of chemically usable feedstock and fuel are central goals for establishing a carbon neutral fuel cycle The role of solvent Molecule's, in catalytic processes is little understood, although solvent-solute interactions can strongly influence activated intermediate species. We use vibrational spectroscopy of mass selected Au(CO2)(n)(-) cluster ions to probe the solvation of AuCO2- as a model for a reactive intermediate in the reductive activation of a CO2 ligand by a single atom catalyst For the first few solvent molecules, solvation of the complex preferentially occurs at the CO2 moiety, enhancing reductive activation through polarization of the excess charge onto the partially reduced ligand. At higher levels of solvation, direct interaction of additional Solvent molecules with the Au atom diminishes reduction. The results show' how the solvation environment can enhance or diminish the effects of a catalyst, offering design criteria for single atom 'catalyst engineering.