Unlocking the Potential of Pulsed Electrolysis: Mechanisms for Improved CO ₂ Electroreduction in GDE Systems

We demonstrate that pulsed electrolysis can unlock higher performance in CO2 electroreduction (CO2ER) on gas diffusion electrodes (GDEs), which we find are limited by cation-induced CO2 depletion and reduced Faradaic efficiency (FE) at high cathodic potentials. Using continuum-scale modeling, we show that pulsing strategies significantly enhance current density compared to steady-state operation at the same mean potential. Thicker catalyst layers (CLs) particularly benefit from pulsed electrolysis, achieving higher current densities near the gas/liquid interface along with overall improvements in Faradaic and cathodic efficiency compared to constant-potential systems. This is caused by the prolonged time for the cations to transport back to and block the catalytic surface, which improves CO2 accessibility. Tuning the pulse parameters, especially with unequal durations, results in a similar current density as a constant potential system, but with better Faradaic and cathodic efficiency. These findings underscore pulsed electrolysis as a scalable and effective method to enhance CO2ER performance in GDE systems, offering practical improvements for industrial applications.