Multiliter-Scale Photosensitized Dimerization of Isoprene to Sustainable Aviation Fuel Precursors

Synthetic routes to sustainable aviation fuels are needed to mitigate the environmental impacts of the aviation sector. Among several emerging methods, the use of light-driven reactions benefits from milder conditions and the possibility of using sunlight to directly irradiate reactants or, alternatively, to power LEDs with a high and constant light intensity. Dinaphthylketone-photosensitized dimerization of isoprene can afford C₁₀ cycloalkenes that, after hydrogenation, meet the required properties for jet fuels (strongly resembling Jet-A). Isoprene can be photobiologically produced by metabolically engineered cyanobacteria from the conversion of CO₂ and water by utilizing solar light, contributing to a carbon-neutral process. The scale-up of such a combined photobiological-photochemical route is essential to bring it closer to the commercial level. Herein, we present the optimization and scale-up of the photosensitized dimerization of isoprene. By designing different reactor setups, flow versus no-flow conditions, and LED lamps (λ_max = 365 nm) versus sunlight as the light source, we reached a 2.6 L scale able to produce 61 mL of isoprene dimers per hour, which represents a 14-fold higher productivity compared to our previous results at a smaller scale. We also demonstrated a continuous feed process that converted isoprene into dimers with a 95% yield under LED irradiation. These advancements highlight the potential of light-driven processes to contribute to the energy transition and production of sustainable aviation fuels, making them more viable for commercial use and significantly reducing the environmental impact of the aviation sector.