Cobaloxime-based homogeneous and metal-organic framework photocatalytic systems for selective reduction of acetylene to ethylene

The semi-hydrogenation of acetylene to ethylene in ethylene-rich gas streams is an industrially important chemical reaction for producing polymer-grade ethylene. Traditional thermocatalytic routes for acetylene reduction to ethylene, despite progress, still require high temperatures and high H2 consumption, possess low selectivity, and use a noble metal catalyst. Light-powered strategies are starting to emerge, given that they have the potential to use directly the abundant and sustainable solar irradiation. Here we report >99.9% selective, visible-light powered, catalytic conversion of acetylene to ethylene. Our catalyst is a homogeneous molecular cobaloxime that operates in tandem with a photosensitizer at room temperature and bypasses the use of non-environmentally friendly and flammable H2 gas feed. The reaction proceeds through a cobalt-hydride intermediate with nearly 100% conversion of acetylene under competitive (ethylene co-feed) conditions after only 50 minutes, and with no evolution of H2 or overhydrogenation to ethane. We further incorporate the cobaloxime as linker in a metal-organic framework; the result is a heterogeneous catalyst for the conversion of acetylene under competitive (ethylene co-feed) conditions that can be recycled up to six times and remains catalytically active for 48 hours, before significant loss of performance is observed.