Atomic dynamics of electrified solid-liquid interfaces in liquid-cell TEM

Electrified solid-liquid interfaces (ESLIs) play a key role in various electrochemical processes relevant to energy^1-5, biology⁶ and geochemistry⁷. The electron and mass transport at the electrified interfaces may result in structural modifications that markedly influence the reaction pathways. For example, electrocatalyst surface restructuring during reactions can substantially affect the catalysis mechanisms and reaction products^1-3. Despite its importance, direct probing the atomic dynamics of solid-liquid interfaces under electric biasing is challenging owing to the nature of being buried in liquid electrolytes and the limited spatial resolution of current techniques for in situ imaging through liquids. Here, with our development of advanced polymer electrochemical liquid cells for transmission electron microscopy (TEM), we are able to directly monitor the atomic dynamics of ESLIs during copper (Cu)-catalysed CO₂ electroreduction reactions (CO₂ERs). Our observation reveals a fluctuating liquid-like amorphous interphase. It undergoes reversible crystalline-amorphous structural transformations and flows along the electrified Cu surface, thus mediating the crystalline Cu surface restructuring and mass loss through the interphase layer. The combination of real-time observation and theoretical calculations unveils an amorphization-mediated restructuring mechanism resulting from charge-activated surface reactions with the electrolyte. Our results open many opportunities to explore the atomic dynamics and its impact in broad systems involving ESLIs by taking advantage of the in situ imaging capability.