Structural Evolution of Cu/ZnO Catalysts during Water-Gas Shift Reaction: An In Situ Transmission Electron Microscopy Study

Supported metal catalysts experience significant structural evolution during the activation process and reaction conditions, which is critical to achieve a desired active surface and interface enabling efficient catalytic processes. However, such dynamic structural information and related mechanistic understandings remain largely elusive owing to the limitation of real-time capturing dynamic information under reaction conditions. Here, using in situ environment transmission electron microscopy, we demonstrate the atomic-scale structural evolution of the model Cu/ZnO catalyst under relevant water-gas shift reaction (WGSR) conditions. Under a CO gas environment, Cu nanoparticles decompose into smaller Cu species and redistribute on ZnO supports with either the crystalline Cu2O or amorphous CuOx phase due to a strong CO–Cu interaction. In addition, we visualize various metal–support interactions between Cu and ZnO under reaction conditions, e.g., ZnO clusters precipitating on Cu nanoparticles, which are critical to understand active sites of Cu/ZnO as catalysts for WGSR. These in situ atomic-scale observations highlight the dynamic interplays between Cu and ZnO that can be extended to other supported metal catalysts.