Abstract
The present study highlights the importance of the net density of charge carriers at the ground state on photocatalytic activity of the faceted particles, which can be seen as a highly underexplored problem. To investigate it in detail, we have systematically doped {1 0 1} enclosed anatase nanoparticles with Gd3+ ions to manipulate the charge carrier concentration. Furthermore, control experiments using an analogical Nb5+ doped sample were performed to discuss photocatalytic activity in the increased range of free electrons. Overall results showed significant enhancement of phenol degradation rate and coumarin hydroxylation, together with an increase of the designed Gd/Ti ratio up to 0.5 at. %. Simultaneously, the mineralization efficiency, measured as a TOC reduction, was controlled between the samples. The observed activity enhancement is connected with the controlled decrease of the donor state density within the materials, being the net effect of the spontaneously present defects and introduced dopants, witch reduce hydroxylation and the hole trapping ability of the {1 0 1} facets. This allows to fine-tune multi-/single-electron processes occurring over the prepared samples, leading to clear activity maxima for 4-nitrophenol reduction, H2O2 generation, and ·OH formation observed for different donor densities. The optimized material exceeds the activity of the TiO2 P25 for phenol degradation by 52% (377% after surface normalization), showing its suitable design for water treatment. These results present a promising approach to boost photocatalyst activity as the combined result of the exposed crystal facet and dopant-optimized density of ground-state charge carriers.