The visible light activity of TiO

Se⁴⁺ and N³⁻ ions were used as codopants to enhance the photocatalytic activity of TiO₂ under sunlight irradiation. The Se/N codoped photocatalysts were prepared through a simple wet-impregnation method followed by heat treatment using SeCl₄ and urea as the dopant sources. The prepared photocatalysts were well characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-diffuse reflectance spectroscopy (UV-DRS), scanning electron microscopy (SEM) and Raman spectroscopy. The codoped samples showed photoabsorption in the visible light range from 430 nm extending up to 580 nm. The photocatalytic activity of the Se/N codoped photocatalysts was evaluated by degradation of 4-nitrophenol (4-NP). The degradation of 4-NP was highly increased for the Se/N codoped samples compared to the undoped and single doped samples under both UV-A and sunlight irradiation. Aiming to determine the electronic structure and dopant locations, quantum chemical modeling of the undoped and Se/N codoped anatase clusters was performed using Density Functional Theory (DFT) calculations with the hybrid functional (B3LYP) and double-zeta (LanL2DZ) basis set. The results revealed that Se/N codoping of TiO₂ reduces the band gap due to mixing of N2p with O2p orbitals in the valence band and also introduces additional electronic states originating from Se3p orbitals in the band gap.

Molecular Modeling methods play a very important role in TiO₂ photocatalysis. Recent advances in TiO₂ photocatalysis have produced a number of interesting surface phenomena, reaction products, and various novel visible light active photocatalysts with improved properties. Quantum mechanical calculations appear promising as a means of describing the mechanisms and the product distributions of the photocatalytic degradation reactions of organic pollutants in both gas and aqueous phases. Since quantum mechanical methods utilize the principles of particle physics, their use may be extended to the design of new photocatalysts. This review introduces molecular modeling methods briefly and emphasizes the use of these methods in TiO₂ photocatalysis. The methods used for obtaining information about the degradabilities of the pollutant molecules, predicting reaction mechanisms, and evaluating the roles of the dopants and surface modifiers are explained.

The kinetics of the photocatalytic degradation of 10 different dichlorophenols and dichloroanilines have been investigated experimentally and theoretically. With the intention of finding certain molecular indices in order to determine the degradation rates of aromatic pollutants, geometry optimizations of the compounds have been performed with the semiempirical PM3 method. The molecular orbital calculations have been carried out by an SCF method using the RHF formalism. The correlations between the apparent first-order rate constants and the calculated molecular properties of the compounds have been examined. Four different structure–activity relationships have been developed expressing the logarithms of the rate constants in terms of the Hammett constants, electron densities of the substituents, the coefficients and the energies of the highest occupied molecular orbitals HOMO, and 1-octanol/water partition coefficients log K _OW.