The Influence of Mesoscopic Surface Structure on the Electrocatalytic Selectivity of CO₂ Reduction with UHV-Prepared...

The key role of morphological defects (e.g., irregular steps and dislocations) on the selectivity of model Cu catalysts for the electrocatalytic reduction of CO₂ (CO₂RR) is illustrated here. Cu(111) single-crystal surfaces prepared under ultrahigh vacuum (UHV) conditions and presenting similar chemical and local microscopic surface features were found to display different product selectivity during the CO₂RR. In particular, changes in selectivity from hydrogen-dominant to hydrocarbon-dominant product distributions were observed based on the number of CO₂RR electrolysis pretreatment cycles performed prior to a subsequent UHV surface regeneration treatment, which lead to surfaces with seemingly identical chemical composition and local crystallographic structure. However, significant mesostructural changes were observed through a micron-scale microscopic analysis, including a higher density of irregular steps on the samples producing hydrocarbons. Thus, our findings highlight that step edges are key for C-C coupling in the CO₂RR and that not only atomistic but also mesoscale characterization of electrocatalytic materials is needed in order to comprehend complex selectivity trends.