Synthesis of Fe, Mn and Cu modified TiO2 photocatalysts for photodegradation of Orange II

Abstract

The residual dyes from different sources are considered a wide variety of organic pollutants introduced into the natural water resources. One of the main sources with severe pollution problems worldwide is the textile industry and its dye-containing wastewaters. The aim of this study was the photocatalytic degradation of the azoic dye “Orange II” using Mn, Cu and Fe modified titania. The catalysts were prepared by two different methods, sol–gel and an impregnation method in a commercial titania (Degussa P25), after drying the samples were calcined at 400°C. The samples were characterized by BET method for surface area measurement (SBET), XRD, Raman spectroscopy, XPS, UV–vis spectroscopy by diffuse reflectance technique and its photocatalytic activity was evaluated in the degradation of the azo dye Orange II in aqueous solutions using the Langmuir–Hinshelwood model. The catalysts prepared by sol–gel method exhibit a larger surface area than the prepared by impregnation and the introduction of the oxides leads to a slight reduction of SBET. The sol–gel samples show lower photoactivity than the impregnated samples due to the presence of both anatase and rutile phases in these powders, the phase junction anatase–rutile facilitate transfer of the photogenerated electron from the conduction band of the rutile phase to the trapping sites on the anatase surface and prevents the electron–hole recombination and allows the holes generated to move to the surface of the catalyst. XRD, Raman, XPS and UV–Vis data show that the metallic cations are incorporated in the titania lattice in greater extend in SG samples while remain dispersed on the surface in impregnated samples. Although the entrance of metallic cations in solid solution enhance the photocatalytic activity due to the enhanced formation of electrons–hole pairs, at a high doping content, a large number of structural defects are induced serving as a recombination center of electron–hole pairs and sol–gel samples show higher photoactivity than impregnated samples, except in the case of Fe modified samples that shows the higher red shift with Eg=1.8eV and compensate the induced recombination center of electron–hole pairs.