Oxygen‐Deficient Dumbbell‐Shaped Anatase TiO2−x Mesocrystals with Nearly 100 % Exposed {101} Facets: Synthesis, Growth Mechanism, and Photocatalytic Performance.

The development of hierarchical TiO2 superstructures with new morphologies and intriguing photoelectric properties for utilizing solar energy is known to be an effective approach to alleviate the serious problems of environmental pollution. Herein, unique oxygen‐deficient dumbbell‐shaped anatase TiO2−x mesocrystals (DTMCs) enclosed by nearly 100 % {101} facets were readily synthesized by mesoscale transformation in TiCl3/acetic acid (HAc) mixed solution, followed by calcination under vacuum. These mesocrystals exhibited much higher photoreactivity toward removing the model pollutants methyl orange and CrVI than truncated tetragonal bipyramidal anatase nanocrystals (TNCs), anatase mesocrystals built from truncated tetragonal bipyramidal anatase nanocrystals (TTMCs), and anatase mesocrystals constructed by anatase nanocrystals with nearly 100 % exposed {101} facets (TMCs), revealing that both the oxidation and reduction abilities of anatase TiO2 were simultaneously enhanced upon fabricating an oxygen‐deficient mesocrystalline architecture with about 100 % exposed {101} facets. Further characterization illustrated that such an enhancement of photoreactivity was mainly due to the strengthened light absorption, boosted charge carrier separation, and nearly 100 % exposed {101} facets of the oxygen‐deficient dumbbell‐shaped anatase mesocrystals. This work will be useful for guiding the synthesis of oxygen‐deficient ordered superstructures of metal oxides with desired morphologies and exposed facets for promising applications in environmental remediation. Hierarchical TiO2 superstructures: Unique oxygen‐deficient dumbbell‐shaped anatase TiO2−x mesocrystals (DTMCs) enclosed by nearly 100 % {101} crystal facets are successfully synthesized by mesoscale transformation in TiCl3/acetic acid mixed solution and subsequent calcination under vacuum. These mesocrystals exhibit enhanced photocatalytic activity toward removing the pollutants methyl orange (MO) and CrVI. [ABSTRACT FROM AUTHOR]