Atomistic Observation of Temperature-Dependent Defect Evolution within Sub-stoichiometric WO_3–x Catalysts

Tunable crystalline defects endow WO_3–x catalysts with extended functionalities for a broad range of photo- and electric-related applications. However, direct visualization of the defect structures and their evolution mechanism is lacking. Herein, aberration-corrected and in situ transmission electron microscopy was complemented by theoretical calculations to investigate the effect of temperature on the defect evolution behavior during hydrogenation treatment. Low processing temperature (100–300 °C) leads to the occurrence of randomly distributed oxygen vacancies within WO_3–x nanosheets. At higher temperatures, oxygen vacancies become highly mobile and aggregate into stacking faults. Planar defects are prone to nucleate at the surface and develop in a zigzag form at 400 °C, while treating at 500 °C promotes the growth of {200}-type stacking faults. Our work clearly establishes that the atomic configuration of the defects in WO_3–x samples could be manipulated by regulating the hydrogenation temperature. This study not only expands our understanding of the structure–function relationships of sub-stoichiometric tungsten oxides but also unlocks their full potential as advanced catalysts by tuning stoichiometry in a controlled manner.