Free energy landscape approach to aid pure phase synthesis of transition metal (X=Cr, Mn and Fe) doped bismuth titanate (Bi2Ti2O7)

•Stability analysis and electronic structure determination.•Explicit free energy dependence of pure phase synthesis.•Systematic prediction of effective growth conditions.•Enhanced optical absorbance by cation manipulation.

A density functional theory study of Cr, Mn and Fe substitutions in Bi2Ti2O7 (BTO) photocatalysts is presented. We performed a stability analysis from our total energy calculations and have determined formations of dopant inspired phases are detrimental to the overall photocatalytic performance of X-doped BTO. From our calculated formation energies and electronic structures it is shown that X substitution of Ti is least stable and should be associated with formation of secondary phases more so than X substitution of Bi. This result contradicts the many experimental studies which suggest transition metal dopants always substitute Ti in BTO, but on the other hand, explains the poor photocatalytic response beyond what has become known as the critical dopant concentration.