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 energy1-5, 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 products1-3. 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.

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 interfaces1-5. Despite their ubiquitous presence, directly probing the dynamic action of mismatch dislocations has been unachievable owing to their buried nature. Here, using the interfacial transformation of copper oxide to copper as an example, we demonstrate the role of mismatch dislocations in modulating oxide-to-metal interfacial transformations in an intermittent manner, by which the lateral flow of interfacial ledges is pinned at the core of mismatch dislocations until the dislocation climbs to the new oxide/metal interface location. Together with atomistic calculations, we identify that the pinning effect is associated with the non-local transport of metal atoms to fill vacancies at the dislocation core. These results provide mechanistic insight into solid-solid interfacial transformations and have substantial implications for utilizing structural defects at buried interfaces to modulate mass transport and transformation kinetics.

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. These results provide a mechanistic detail of ordering transformation phenomena which are widely relevant to nanoalloys as chemical ordering occurs in most multicomponent materials under suitable environmental bias.

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 H2 gas, a reaction pathway of CuO → monoclinic m-Cu4 O3 → Cu2 O is demonstrated and identifies interfacial reaction fronts at the atomic scale, where the Cu2 O/m-Cu4 O3 interface shows a diffuse-type interfacial transformation; while the lateral flow of interfacial ledges appears to control the m-Cu4 O3 /CuO transformation. Together with atomistic modeling, it is shown that such a multi-interface transformation results from the surface-reaction-induced formation of oxygen vacancies that diffuse into deeper atomic layers, thereby resulting in the formation of the lower oxides of Cu2 O and m-Cu4 O3 , and activate the interfacial transformations. These results demonstrate the lively dynamics at the reaction fronts of the multiple interfaces and have substantial implications for controlling the microstructure and interphase boundaries by coupling the interplay between the surface reaction dynamics and the resulting mass transport and phase evolution in the subsurface and bulk.

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. Based on atomic scale observations of the upward growth at the nanowire tip, oscillatory downward growth of atomic layers on the nanowire sidewall and the parabolic kinetics of lengthening, bicrystal grain boundary diffusion is the mechanism by which Cu ions are delivered from the nanowire root to the tip. Together with density-functional theory calculations, we further show that the asymmetry in the corner-crossing barriers promotes the unidirectional oxide growth by hindering the transport of Cu ions from the nanowire tip to the sidewall facets. We expect the broader applicability of these results in manipulating the growth of nanostructured oxides by controlling the bicrystal grain boundary structure that favors anisotropic diffusion for unidirectional, one-dimensional crystal growth for nanowires or isotropic diffusion for two-dimensional platelet growth.

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 in situ observations of the oxidation of EGaIn nanoparticles by ambient air under high-energy electron beam irradiation. Our findings demonstrate that uneven oxide shell growth, driven by inward diffusion of adsorbed O species, creates unbalanced stresses. This compels the liquid metal to deform toward regions with slower oxide growth, resulting in shell rupture and allowing the liquid metal core to flow out. This process initiates top-down self-similar replication of the core-shell liquid metal nanoparticles, causing larger particles to break down into smaller particles. Additionally, internal oxidation triggers phase separation within the liquid core, ultimately leading to the pulverization of the liquid metal into finer solid particles rich in indium. These mechanistic insights into the oxidation behavior of the liquid metal hold practical implications for leveraging this process to reconfigure EGaIn nanoparticles for various applications.

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. All these substeps can be traced back to the progressively increased concentration and activity of O vacancies in the surface and subsurface of the oxide, thereby leading to the self-accelerated oxide reduction. These results demonstrate the microscopic details that may have a broader applicability in modulating various redox processes.

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. These results demonstrate the propagation of the surface reaction dynamics into the deeper layers in inducing nonstoichiometry in the subsurface and have significant implications in modulating various chemical processes involving surface-subsurface mass transport such as heterogeneous catalysis, oxidation, corrosion and carburization.

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. Using dynamic, atomic-scale electron microscopy observations and theoretical modeling, we delineate the atomic-scale mechanisms associated with the nucleation, rotation and amorphization-crystallization oscillations of the Au clusters. We expect broader applicability of the results because the phase separation process is dictated by the inherent asymmetric adatom-substrate exchange barriers for separating dissimilar atoms in multicomponent materials.