Kinetic study of p-nitrophenol photodegradation with modified TiO2 xerogels

TiO2 xerogels were sensitized in one step by the in situ introduction of nickel (II) tetra(4-carboxyphenyl)porphyrin (TCPPNi) into the TiO2 matrix during sol–gel synthesis. Crystalline photoactive phase TiO2-anatase was obtained without high thermal treatments and was determined by X-ray diffraction. The presence of TCPPNi in TiO2 xerogels was established by DR-UV/Vis and FT-IR spectroscopy. The introduction of porphyrin led to a diminution of the specific surface area of TiO2 xerogels, and this diminution was analyzed by nitrogen adsorption–desorption. The particle size was estimated by SEM. The xerogel surface charge state, which influences the interactions between pollutant and TiO2, was determined by measurement of the point of zero charge. The photoactivity of xerogels was evaluated for p-nitrophenol degradation in aqueous medium at 20 ◦C. Results showed that porphyrin doped TiO2 degraded more than 40% of the p-nitrophenol whereas non doped TiO2 xerogel degraded only 10% of the compound. Moreover, porphyrin was found to improve the photoactivity of TiO2 xerogels in a similar way to UV-A pretreatment. A kinetic study of p-nitrophenol degradation was then performed. Results showed that one type of active site corresponding to the hole of electron–hole pairs was created at the TiO2 surface by light and that the rate determining step was the reaction between the adsorbed
p-nitrophenol molecule and the adsorbed OH• radical. The apparent activation energy was found to be equal to 12 kJ mol−1.