Structural and photocatalytic properties of perovskite-type (La,Ca)Ti(O,N)(3) prepared from A-site deficient precursors

Two series of oxide precursors for perovskite-type (La,Ca)Ti(O,N)(3) were prepared by adding Ca2+ to A-site deficient LaTiO3.5 heterogeneously (Ca2+-backfilling) or by substituting Ca2+ for La3+ in stoichiometric LaTiO3.5 homogeneously (Ca2+-substitution). Activity of the resultant (La,Ca)Ti(O,N)(3) for photocatalytic O-2 evolution was tested in the presence of an electron acceptor (Ag+) and a superior activity of Ca2+-backfilled LaTiO2N compared to Ca2+-substituted LaTiO2N and unsubstituted LaTiO2N was demonstrated. X-ray diffraction patterns of the precursor oxides revealed a higher degree of crystallinity in La1-xTiO3.5-3x/2 compared to La1-xCaxTiO3.5-x/2. The higher crystallinity in La1-xTiO3.5-3x/2 resulted in lower Ti3+ defect formation during the ammonolysis reaction. This was evidenced by the lower background absorption of the diffuse reflectance spectra in Ca2+-backfilled compared to Ca2+-substituted LaTiO2N. Structural refinement of the diffraction patterns revealed growing crystal sizes with the Ca2+ content, which was more pronounced for Ca2+-backfilled than for Ca2+-substituted LaTiO2N. Thus, the enhanced photocatalytic activity of Ca2+-backfilled LaTiO2N was related to the quality of the precursor oxides, which influenced the defect concentrations and crystallite sizes of the resulting oxynitrides.