Reversible metal cluster formation on Nitrogen-doped carbon controlling electrocatalyst particle size with subnanometer accuracy

Copper and nitrogen co-doped carbon catalysts exhibit a remarkable behavior during the electrocatalytic CO₂ reduction (CO₂RR), namely, the formation of metal nanoparticles from Cu single atoms, and their subsequent reversible redispersion. Here we show that the switchable nature of these species holds the key for the on-demand control over the distribution of CO₂RR products, a lack of which has thus far hindered the wide-spread practical adoption of CO₂RR. By intermitting pulses of a working cathodic potential with pulses of anodic potential, we were able to achieve a controlled fragmentation of the Cu particles and partial regeneration of single atom sites. By tuning the pulse durations, and by tracking the catalyst's evolution using operando quick X-ray absorption spectroscopy, the speciation of the catalyst can be steered toward single atom sites, ultrasmall metal clusters or large metal nanoparticles, each exhibiting unique CO₂RR functionalities.