Operando probing dynamic migration of copper carbonyl during electrocatalytic CO2 reduction

Single crystals and shape-controlled nanocrystals are well known to exhibit facet-dependent catalytic properties. However, few studies have investigated how those nanocrystals evolve and (de)activate during reactions, calling for the development of nanoscale time-resolved operando methods. In this context, we have designed Cu nanocubes as a model system to elucidate the underlying driving force of dynamic nanocatalyst reconstruction during the CO₂ reduction reaction (CO₂RR). Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) and synchrotron-based X-ray spectroscopy reveal the size- and potential-dependent complete transformation from (100)-oriented Cu@Cu₂O nanocubes to polycrystalline metallic Cu nanograins under CO₂RR conditions. In addition, machine learning-assisted operando four-dimensional STEM reveals that large Cu nanograins derived from nanocubes form mainly crystalline domains, while their smaller counterparts are more amorphous due to faster evolution kinetics. In situ Raman spectroscopy and density functional theory calculations suggest that CO drives the ejection of single Cu atoms, resulting in few-nanometre Cu clusters and the surface migration of highly mobile copper carbonyl (Cu–CO) species. Combined, these multimodal operando methods and theoretical approaches pave the way for understanding the complex structural evolution of energy-related nanocatalysts under electrochemical conditions.