Steering the structure and selectivity of CO2 electroreduction catalysts by potential pulses

Convoluted selectivity trends and a missing link between reaction product distribution and catalyst properties hinder practical applications of the electrochemical CO2 reduction reaction (CO2RR) for multicarbon product generation. Here we employ operando X-ray absorption and X-ray diffraction methods with subsecond time resolution to unveil the surprising complexity of catalysts exposed to dynamic reaction conditions. We show that by using a pulsed reaction protocol consisting of alternating working and oxidizing potential periods that dynamically perturb catalysts derived from Cu2O nanocubes, one can decouple the effect of the ensemble of coexisting copper species on the product distribution. In particular, an optimized dynamic balance between oxidized and reduced copper surface species achieved within a narrow range of cathodic and anodic pulse durations resulted in a twofold increase in ethanol production compared with static CO2RR conditions. This work thus prepares the ground for steering catalyst selectivity through dynamically controlled structural and chemical transformations.