Electrocatalytic Scission of Unactivated C(sp 3 )–C(sp 3 ) Bonds through Real-Time Manipulation of Surface-Bound Intermediates

Electrocatalysis plays a critical role in future technologies for energy storage and sustainable synthesis, but the scope of reactions achievable using electricity remains limited. Here, we demonstrate an electrocatalytic approach to cleave the C(sp3)–C(sp3) bond in ethane at room temperature over a nanoporous Pt catalyst. 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, oxidative C–C bond fragmentation, and reductive methane desorption. Importantly, our approach allows 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 electrocatalytic energy storage technologies.