Electrocatalytic Scission of Unactivated C(sp3)−C(sp3) Bonds Through Real-Time Manipulation of Surface-Bound Intermediates

We demonstrate an electrocatalytic approach to cleave the C(sp3)-C(sp3) bond in ethane at room temperature. This reaction is enabled by time-dependent electrode potential sequences, combined with monolayer-sensitive in-situ analysis, which allows us to gain independent control over ethane adsorption, C-C bond fragmentation, and methane desorption. Importantly, our approach allowed us to vary the electrode potential to promote the fragmentation of ethane after it is bound to the catalyst surface, resulting in unprecedented control over the selectivity of this alkane transformation reaction. Steering the transformation of intermediates after adsorption constitutes an underexplored lever of control in catalysis. As such, our findings widen the parameter space for catalytic reaction engineering and open the door to future sustainable synthesis and energy storage technologies.