Perovskite-type LaTiO2N oxynitrides for solar water splitting: Influence of the synthesis conditions

摘要

Oxynitrides with the nominal composition LaTiO2N were prepared from a La2Ti2O7 precursor by thermal ammonolysis of the oxide under an NH3 flow for different durations t (4-30 h). X-ray diffraction (XRD) indicated that phase-pure LaTiO2N samples were obtained when t > 13 h. The material was further characterised by scanning electron microscopy (SEM), surface area measurements based on the BET method, thermogravimetric analysis (TGA) and UV-visible diffuse reflectance spectroscopy (DRS). The powders displayed an increased crystallite size and a decreased surface area with increasing t. The ratio of N/(N+0) increased with t from 0.22-0.27. Correlated to this nitrogen increase, a small variation of the bandgap energy was observed from 2.19 to 2.12 eV with t. All LaTiO2N samples oxidised H2O into O2 in the presence of an electron acceptor (Ag~(-1)). The O2 evolution was increased from 12 umol/h (t = 13 h) to 22-24 umol/h (16 h < r < 30 h). It was found that the nitrogen content and the amount of defects played a key role in the photocatalytic O2 evolution.