Plasmonic photosynthesis of C1–C3 hydrocarbons from carbon dioxide assisted by an ionic liquid

Abstract Photochemical conversion of CO 2 into fuels has promise as a strategy for storage of intermittent solar energy in the form of chemical bonds. However, higher-energy-value hydrocarbons are rarely produced by this strategy, because of kinetic challenges. Here we demonstrate a strategy for green-light-driven synthesis of C 1 –C 3 hydrocarbons from CO 2 and H 2 O. In this approach, plasmonic excitation of Au nanoparticles produces a charge-rich environment at the nanoparticle/solution interface conducive for CO 2 activation, while an ionic liquid stabilizes charged intermediates formed at this interface, facilitating multi-step reduction and C–C coupling. Methane, ethylene, acetylene, propane, and propene are photosynthesized with a C 2+ selectivity of ~50% under the most optimal conditions. Hydrocarbon turnover exhibits a volcano relationship as a function of the ionic liquid concentration, the kinetic analysis of which coupled with density functional theory simulations provides mechanistic insights into the synergy between plasmonic excitation and the ionic liquid.