The Native Oxide Skin of Liquid Metal Ga Nanoparticles Prevents Their Rapid Coalescence during Electrocatalysis

Liquid metals (LMs) have been used in electrochemistry since the 19th century, but it is only recently that they have emerged as electrocatalysts with unique properties, such as inherent resistance to coke poisoning, which derives from the dynamic nature of their surface. The use of LM nanoparticles (NPs) as electrocatalysts is highly desirable to enhance any surface-related phenomena. However, LM NPs are expected to rapidly coalesce, similarly to liquid drops, which makes their implementation in electrocatalysis hard to envision. Herein, we demonstrate that liquid Ga NPs (18 nm, 26 nm, 39 nm) drive the electrochemical CO 2 reduction reaction (CO 2 RR) while remaining well-separated from each other. CO is generated with a maximum faradaic efficiency of around 30% at −0.7 V RHE, which is similar to that of bulk Ga. The combination of electrochemical, microscopic, and spectroscopic techniques, including operando X-ray absorption, indicates that the native oxide skin of the Ga NPs is still present during CO 2 RR and provides a barrier to coalescence during operation. This discovery provides an avenue for future development of Ga-based LM NPs as a new class of electrocatalysts.