DENSITY FUNCTIONAL STUDY OF STRUCTURAL AND ELECTRONIC PROPERTIES OF Ca AND Mg DOPED TiO2

Abstract

The scarcity of affordable and environment-friendly sources of energy has led to emergence of photocatalysis to mitigate this problem. This is especially so if the photo catalysts are active in as much a wide region of the solar energy spectrum as possible. Environment-friendly, non-toxic and economical photocatalysts would find application in water treatment, providing another solution to the problem of clean water for domestic use. Of many materials available for photocatalysis is Titanium (IV) oxide (TiO2). It possesses many merits such as low cost, high photocatalytic activity, non-toxicity and high availability. However, drawbacks that limit its application include its optical absorption that falls in the ultraviolet part of the electromagnetic spectrum and rapid electron-hole recombination, which limits its photoquantum efficiency. To extend the optical absorption to a wider region of the solar energy spectrum, various dopants have been added to the oxide. In this study, the effect of doping rutile TiO2 with alkaline earth metals Ca and Mg is investigated using the Density Functional Theory (DFT) method as implemented in the Quantum ESPRESSO simulation package, treating the exchange correlation potential with the Generalised Gradient Approximation. The optimized cell parameters for pure rutile crystal system are 𝑎 = 𝑏 = 4.603Å 𝑐 = 2.992Å, with a volume of 63.393 (Å)3 . On doping there is a slight expansion of the crystal structure and its volume slightly increases by 8.753 (Å) 3 and 28.816 (Å) 3 with Mg and Ca doping respectively. The calculated band gap of undoped rutile is 1.8 eV. Mg and Ca doping raises the valence band edge by 0.2 eV in both Ca and Mg doped rutile. Dopant inter band and intra band states are observed that would be useful in mitigating against charge recombination hence enhancing the efficiency of the photocatalysts. Isolated O 2p states are observed in the Projected Density of States (PDOS) of the doped systems which are normally attributed to enhanced optical absorption of photocatalysts in the visible region. Alkaline earth metal doping of TiO2 rutile modifies the structural and electronic properties of rutile TiO2 in a manner that would make it a more efficient photocatalyst. Co-doping with the alkaline metal dopants could be attempted to investigate the combined effect.