The extraordinary catalytic properties of enzymes are derived not only from their catalytic groups but also the unique properties of the active site. Tuning the microenvironment of synthetic catalysts is expected to enhance their performance if effective strategies can be developed. Interfacially cross-linked reverse micelles were prepared from three different cross-linkable surfactants. Pd nanoparticles were deposited in the core of the micelle for the catalytic hydrogenation of bicarbonate and CO2. The catalytic performance was found to depend heavily on the nature of the headgroup of the surfactant. Quaternary ammonium-based surfactants through ion exchange could bring bicarbonate to the catalytic center, whereas tertiary amine-based surfactants worked particularly well in CO2 hydrogenation, with turnover numbers an order of magnitude higher than that of commercially available Pd/C. The amines were proposed to bring CO2 to the proximity of the catalysts through reversible formation of carbamate, in the nanospace of the hydrophilic core of the cross-linked reverse micelle. In the bicarbonate reduction, additional improvement of the catalysts was achieved through localized sol-gel synthesis that introduced metal oxide near the catalytic metal.
Keywords: catalysis; cross-linking; hydrogenation; nanoparticle; reverse micelle.