Mechanochemical reaction of TiO₂ with β-alanine for the preparation of visible light active nitrogen doped titania: adsorption and kinetic studies

摘要

Nitrogen doped TiO₂ (TiO_2−xN_x) with a homogenous anatase phase was synthesized, using β-alanine as a nitrogen precursor and ethanol as a oxygen depriving agent in the concentration range of 0.05, 0.10, 0.15 and 0.2 at% and were characterized by Powder X-ray Diffraction (PXRD), X-ray Photoelectron Spectra (XPS), Scanning Electron Microscope (SEM), Fourier Transform Infrared (FT-IR) and UV–visible Diffused Reflectance Spectroscopic (DRS) techniques. Ethanol deprives the surface oxygen, thereby generating oxygen defects whose concentration was evaluated by FTIR, Photoluminescence (PL) and Electron Spin Resonance (ESR) studies. FTIR analysis reveal that concentration of oxygen vacancies/defects (V_o) decreases as the nitrogen concentration increases leading to the reduction in the Ti–O bond length. This results in a shift of the IR absorption peak towards a low wave number as predicted by simple physical harmonic oscillator model. The Ti 2p_3/2 XPS spectra of TiO_2−xN_x shifts to lower binding energies due to the increase in the electron densities around the Ti atoms indicating the formation of Ti3+ in the doped samples. N₂ adsorption–desorption isotherms measurements show a slight increase in the Brunner–Emmet–Teller (BET) surface area, pore diameter, mesopore volume, while the crystallite size and the morphology were also effected by the nitrogen doping. The equilibrium adsorption of Toluene molecules on the photocatalyst surface follows Langmuir theory and the rate controlling step could be the surface reaction of the adsorbed Toluene molecules.