Light-assisted carbon dioxide reduction in an automated photoreactor system coupled to carbonylation chemistry

Continuous-flow methodologies offer promising avenues for sustainable processing due to their precise process control, scalability, and efficient heat and mass transfer. The small dimensions of continuous-flow reactors render them highly suitable for light-assisted reactions, as can be encountered in carbon dioxide hydrogenations. In this study, we present a reactor system emphasizing reproducibility, modularity, and automation, facilitating streamlined screening of conditions and catalysts for these processes. The proposed commercially available photoreactor, in which carbon dioxide hydrogenation was conducted, features narrow channels with a high-surface area catalyst deposition. Meticulous control over temperature, light intensity, pressure, residence time, and reagent stoichiometry yielded the selective formation of carbon monoxide and methane using heterogeneous catalysts, including a novel variant of ruthenium nanoparticles on titania catalyst. All details on the automation are made available, enabling its use by researchers worldwide. Furthermore, we demonstrated the direct utilization of on-demand generated carbon monoxide in the production of fine chemicals via various carbonylative cross-coupling reactions.