Oxidation-Induced Oxide Shell Rupture and Phase Separation in Eutectic Gallium-Indium Nanoparticles.

Eutectic gallium-indium (EGaIn), a room-temperature liquid metal, has garnered significant attention for its applications in soft electronics, multifunctional materials, energy engineering and drug delivery. A key factor influencing these diverse applications is the spontaneous formation of a native passivating oxide shell that not only encapsulates the liquid metal but also alters the properties from the bulk counterpart. Using environmental scanning transmission electron microscopy, we report observations of the oxidation of EGaIn nanoparticles by ambient air under high-energy electron beam irradiation.

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, biology and geochemistry. 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.

Atomic Dynamics of Multi-Interfacial Migration and Transformations.

Redox-induced interconversions of metal oxidation states typically result in multiple phase boundaries that separate chemically and structurally distinct oxides and suboxides. Directly probing such multi-interfacial reactions is challenging because of the difficulty in simultaneously resolving the multiple reaction fronts at the atomic scale. Using the example of CuO reduction in H gas, a reaction pathway of CuO → monoclinic m-Cu O → Cu O is demonstrated and identifies interfacial reaction fronts at the atomic scale, where the Cu O/m-Cu O interface shows a diffuse-type interfacial transformation; while the lateral flow of interfacial ledges appears to control the m-Cu O /CuO transformation.

Dislocation-induced stop-and-go kinetics of interfacial transformations.

Most engineering materials are based on multiphase microstructures produced either through the control of phase equilibria or by the fabrication of different materials as in thin-film processing. In both processes, the microstructure relaxes towards equilibrium by mismatch dislocations (or geometric misfit dislocations) across the heterophase interfaces. Despite their ubiquitous presence, directly probing the dynamic action of mismatch dislocations has been unachievable owing to their buried nature.

Composition-dependent ordering transformations in Pt-Fe nanoalloys.

SignificanceDynamically understanding the microscopic processes governing ordering transformations has rarely been attained. The situation becomes even more challenging for nanoscale alloys, where the significantly increased surface-area-to-volume ratio not only opens up a variety of additional freedoms to initiate an ordering transformation but also allows for kinetic interplay between the surface and bulk due to their close proximity. We provide direct evidence of the microscopic processes controlling the ordering transformation through the surface-bulk interplay in Pt-Fe nanoalloys and new features rendered by variations in alloy composition and chemical stimuli.

Atomic Origin of the Autocatalytic Reduction of Monoclinic CuO in a Hydrogen Atmosphere.

Reducibility is key for the use of bulk metal oxides in chemical transformations involving redox reactions, but probing microscopic processes of oxide reduction is challenging. This is because the insulating nature of bulk oxides restricts ion and electron spectroscopic measurements of oxide surfaces. Herein, using a combination of environmental transmission electron microscopy and atomistic modeling, we report direct in situ atomic-scale observations of the surface and subsurface dynamics and show that the hydrogen-induced CuO reduction occurs through the receding motion of Cu-O/Cu bilayer steps at the surface, the formation of the partially reduced CuO superstructure by the self-ordering of O vacancies in the subsurface, and the collapse of Cu-O layers in the bulk.

Atomic-scale phase separation induced clustering of solute atoms.

Dealloying typically occurs via the chemical dissolution of an alloy component through a corrosion process. In contrast, here we report an atomic-scale nonchemical dealloying process that results in the clustering of solute atoms. We show that the disparity in the adatom-substrate exchange barriers separate Cu adatoms from a Cu-Au mixture, leaving behind a fluid phase enriched with Au adatoms that subsequently aggregate into supported clusters.

Surface-reaction induced structural oscillations in the subsurface.

Surface and subsurface are commonly considered as separate entities because of the difference in the bonding environment and are often investigated separately due to the experimental challenges in differentiating the surface and subsurface effects. Using in-situ atomic-scale transmission electron microscopy to resolve the surface and subsurface at the same time, we show that the hydrogen-CuO surface reaction results in structural oscillations in deeper atomic layers via the cycles of ordering and disordering of oxygen vacancies in the subsurface. Together with atomistic calculations, we show that the structural oscillations in the subsurface are induced by the hydrogen oxidation-induced cyclic loss of oxygen from the oxide surface.

Atomic-Scale Mechanism of Unidirectional Oxide Growth.

A fundamental knowledge of the unidirectional growth mechanisms is required for precise control on size, shape, and thereby functionalities of nanostructures. The oxidation of many metals results in oxide nanowire growth with a bicrystal grain boundary along the axial direction. Using transmission electron microscopy that spatially and temporally resolves CuO nanowire growth during the oxidation of copper, here we provide direct evidence of the correlation between unidirectional crystal growth and bicrystal grain boundary diffusion.