Micron/nanosized particles of liquid metals possess intriguing properties and are gaining popularity for applications in various research fields. Nevertheless, the knowledge of their chemistry is still very limited compared to that of other classes of materials. In this work, we explore the reactivity of Ga nanoparticles (NPs) toward a copper molecular precursor to synthesize bimetallic Cu−Ga NPs. Anisotropic Cu−Ga nanodimers, where the two segregated domains of the constituent metals share an interface, form as the reaction product. Through a series of careful experiments, we demonstrate that a galvanic replacement reaction (GRR) between the Ga seeds and a copper-amine complex takes place. We attribute the final morphology of the bimetallic NPs, which is unusual for a GRR, to the presence of the native oxide shell around the Ga NPs and their liquid nature, via a mechanism that resembles the adhesion of bulk Ga drops to solid conductors. On the basis of this new knowledge, we also demonstrate that sequential GRRs to include more metal domains are possible. This study illustrates a new approach to the synthesis of Ga-based metal nanoparticles and provides the basis for its extension to many more systems with increased levels of complexity.

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 CO2 reduction reaction (CO2RR) while remaining well-separated from each other. CO is generated with a maximum faradaic efficiency of around 30% at −0.7 VRHE, 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 CO2RR 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.

Solid-state reactions between micrometer-size powders are among the oldest, simplest, and still widely used methods for the fabrication of inorganic solids. These reactions are intrinsically slow because, although the precursorsare “well mixed” at the macroscale, they are highly inhomogeneous at the atomic level. Furthermore, their products are bulk powders that are not suitable for device integration. Herein, we substitute micrometer-size particles with nanocrystals. Scaling down the size of the precursors reduces the reaction time and temperature. More importantly, the final products are nanocrystals with controlled size and shape that can be used as active materials in various applications, including electro- and photocatalysis. The assembly of the nanocrystal precursors as ordered close-packed superlattices enables microscopy studies that deepen the understanding of the solid-state reaction mechanism. We learn that having only one of the two nanocrystal precursors dissolving and diffusing toward the other is crucial to obtain a final nanocrystalline product with homogeneous size and shape. The latter are regulated by the nanocrystal precursor that is the most stable at the reaction temperature. Considering the variety of controlled nanocrystals available, our findings open a new avenue for the synthesis of functional and tunable polyelemental nanomaterials.

Non-noble metal nanocrystals with well-defined shapes have been attracting increasingly more attention in the last decade as potential alternatives to noble metals, by virtue of their Earth abundance combined with...