Unraveling the Impact of Adsorbed Molecules on Photocatalytic Processes: Advancements in Understanding Facet-Controlled Semiconductor Photocatalysts.

This work aims to demonstrate that the Fe 2 O 3 nanocrystals' adsorptive and photocatalytic properties can be adjusted by exposing the crystal facets that are functionalized. To this end, cube- and disc-like structures were synthesized using a metal ion-mediated hydrothermal route. Thereafter, some of the samples were annealed at 500 °C for 3 h. Our paper combines the experimental part with theoretical calculations of the obtained materials' band edge positions. The results reveal that-aside from hematite-the as-synthesized discs also contain γ-FeOOH and β-Fe 2 O 3 phases, which transform into α-Fe 2 O 3 during annealing. The hydrodynamic diameter, zeta potential, and adsorption kinetics measurements show that the cube-like samples exhibit the highest affinity for cationic, whereas the discs have an affinity for anionic dye. Measurements of the wall zeta potential also reveal that annealing the discs modifies their surface state and ability to adsorb molecules. Photocatalytic tests show that the as-synthesized powders have better photocatalytic performance toward methylene blue decomposition than the annealed ones. The observed small changes in the concentration of the MO during illumination result from the energy band structure of the cube-like crystal orientation.