Anodization of TiB2 monolith rather than Ti0 was employed to prepare boron-doped TiO2 photoelectrochemical (PEC) anode and nanocrystals. The anodization behavior of TiB2 was found to be dependent on the orientation of the crystals and F− ions in the electrolyte. TiB2 orientating in [100] direction after anodization in the presence of F− formed a porous TiO2 layer that can be used as a PEC anode, while TiB2 with exposed (001) facets produced a gel containing Ti species in the electrolyte. The PEC anode or nanocrystals from the gel after hydrothermal treatment was boron-doped TiO2 showing superior photocatalytic performance over the counterpart from Ti0 foil for water splitting or Degussa P25 catalyst for dye degradation, respectively. The anodization of conductive ceramic monolith was demonstrated to be a way of preparing doped semiconductors for enhanced photocatalytic performance.
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