Non-Faradaic Promotion of Ethylene Hydrogenation under Oscillating Potentials.

The acceleration of Faradaic reactions by oscillating electric potentials has emerged as a viable tool to enhance electrocatalysis, but the non-Faradaic dynamic promotion of thermal catalytic processes remains to be proven. Here, we present experimental evidence showing that oscillating potentials are capable of enhancing the rate of ethylene hydrogenation despite no promotion effect being observed under static potentials. The non-Faradaic dynamic enhancement reaches up to 553% on a Pd/C electrode when cycling between -0.25 and 0.55 V under optimized conditions with a frequency of around 0.1 Hz and a duty cycle of 99%. Under those conditions, the catalytic reaction rates were promoted beyond the rate of charge transfer to the electrode surface, confirming the non-Faradaic nature of the process. Experiments in different electrolytes reveal a good correlation between the catalytic enhancement and the double-layer capacitance, a measure for the interfacial electric field strength. Preliminary kinetic data is consistent with cyclic removal of adsorbates from the surface at negative potential and the subsequent adsorption of H and CH and hydrogenation reaction at the positively polarized surface.