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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.

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