Dynamic Surface Evolution of Metal Oxides for Autonomous Adaptation to Catalytic Reaction Environments.

Metal oxides possessing distinctive physical/chemical properties due to different crystal structures and stoichiometries play a pivotal role in numerous current technologies, especially heterogeneous catalysis for production/conversion of high-valued chemicals and energy. To date, many researchers have investigated the effect of the structure and composition of these materials on their reactivity to various chemical and electrochemical reactions. However, metal oxide surfaces evolve from their initial form under dynamic reaction conditions due to the autonomous behaviors of the constituent atoms to adapt to the surrounding environment. Such nanoscale surface phenomena complicate reaction mechanisms and material properties, interrupting the clarification of the origin of functionality variations in reaction environments. In this review, the current findings on the spontaneous surface reorganization of metal oxides during reactions are categorized into three types: 1) the appearance of nano-sized second phase from oxides, 2) the (partial) encapsulation of oxide atoms toward supported metal surfaces, and 3) the oxide surface reconstruction with selective cation leaching in aqueous solution. Then their effects on each reaction are summarized in terms of activity and stability, providing novel insight for those who design metal-oxide-based catalytic materials.