A DFT investigation into the effects of As-doping on the electronic structure and electrochemical activity of pyrite (FeS2).

Abstract Pyrite (FeS2) is a semiconductor mineral with electronic structural properties that are heavily influenced by trace elements in its composition. It has been demonstrated experimentally that the reduction of Fe3+ ions is significantly enhanced in the presence of trace arsenic (As) atoms in FeS2. Using density functional theory calculations, we compare the geometric and electronic structural properties of pure and As-doped (110) pyrite surfaces. The interaction of the Fe3+ ion, a common oxidant of sulfides in acidic solution and acid mine drainage, with the aforementioned surfaces is thoroughly investigated. The findings reveal that the addition of an As atom alters the electronic structure of pyrite and decreases its band gap. The adsorption energy of the Fe3+ ion on As-doped pyrite is greater than that on pure pyrite. The calculated Gibbs free energy changes show that the reduction of Fe3+ to Fe2+ ion on the As-modified surface is thermodynamically more favorable than on pure pyrite.