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 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.
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, herein, direct evidence of the correlation between unidirectional crystal growth and bicrystal grain boundary diffusion is provided. 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, it is shown that 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, it is further shown 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. 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, 1D crystal growth for nanowires or isotropic diffusion for 2D platelet growth is expected.
Significance Dynamically 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.
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