Facet Control of Subunits in Anatase TiO₂ Mesocrystal by Diethanolamine for Enhanced Photocatalytic Activity.

Controllable TiO2 architectures with different facets play a key role in the adjustment of the surface area and charge recombination efficiency in photocatalysts. In this study, we synthesized anatase TiO2 mesocrystals with diethanolamine (DEA, 0-5 mM) as a nontoxic capping agent to control the facet of subunits using hydrothermal method, and determine the effect of DEA on subunits, by-products, and consequent photocatalytic performance of TiO2 mesocrystals. The pure TiO2 was spindle-like shaped mesocrystal having bipyramidal subunits with high portion of {101} facets. As DEA concentration was increased, the percentage of {001} exposed facet of subunits increased, but the number of subunits was gradually reduced. When a large amount of DEA (≥3 mM) was added, TiO2 exhibited single crystals rather than mesocrystal, probably because the long chain of DEA interfered with the oriented attachment of subunits. The photocatalytic activity of the TiO2 improved at 0.5 mM of DEA due to low charge recombination rate by increasing {001} facet. On the other hand, subsequent deterioration with further increase of DEA was attributed to the increased by-products and reduced the number of subunits despite the increase in specific surface area. These results imply that charge separation efficiency, rather than specific surface area, is highly responsible for the photocatalytic activity of TiO2.