Borocarbonitride Layers on Titanium Dioxide Nanoribbons for Efficient Photoelectrocatalytic Water Splitting.

Heterostructures formed by ultrathin borocarbonitride (BCN) layers grown on TiO2 nanoribbons were investigated as photoanodes for photoelectrochemical water splitting. TiO2 nanoribbons were obtained by thermal oxidation of TiS3 samples. Then, BCN layers were successfully grown by plasma enhanced chemical vapour deposition. The structure and the chemical composition of the starting TiS3, the TiO2 nanoribbons and the TiO2-BCN heterostructures were investigated by Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Diffuse reflectance measurements showed a change in the gap from 0.94 eV (TiS3) to 3.3 eV (TiO2) after the thermal annealing of the starting material. Morphological characterizations, such as scanning electron microscopy and optical microscopy, show that the morphology of the samples was not affected by the change in the structure and composition. The obtained TiO2-BCN heterostructures were measured in a photoelectrochemical cell, showing an enhanced density of current under dark conditions and higher photocurrents when compared with TiO2. Finally, using electrochemical impedance spectroscopy, the flat band potential was determined to be equal in both TiO2 and TiO2-BCN samples, whereas the product of the dielectric constant and the density of donors was higher for TiO2-BCN.