Electroenzymatic C–C Bond Formation from CO₂

Over the past decade, there has been significant research in electrochemical reduction of CO₂, but it has been difficult to develop catalysts capable of C–C bond formation. Here, we report bioelectrocatalysis of vanadium nitrogenase from Azotobacter vinelandii, where cobaltocenium derivatives transfer electrons to the catalytic VFe protein, independent of ATP-hydrolysis. In this bioelectrochemical system, CO₂ is reduced to ethylene (C₂H₄) and propene (C₃H₆), by a single metalloenzyme.