Structural, Electronic, and Thermodynamic Properties of the T and B Phases of Niobia: First-Principle Calculations

Different polymorphs of Nb₂O₅ can be obtained depending on the pressure and temperature of calcination leading to different catalytic properties. Two polymorphs of niobia, T-Nb₂O₅ and B-Nb₂O₅, have been investigated by means of density functional/plane waves method. The equation of state predicted that B-Nb₂O₅ phase is more stable than the T-Nb₂O₅ at low temperature; however at high pressure both phases are stable. These results are in good agreement with the available experimental data. The calculated cohesive energies of 6.63 and 6.59 eV·atom^-1 for the B-Nb₂O₅ and T-Nb₂O₅, respectively, also corroborate this conclusion, and it can be compared to the experimental value of 9.56 eV atom^-1 estimated for the most thermodynamically stable phase. The topological analyses based on quantum theory of atoms in molecules (QTAIM) and electron localization function (ELF) were applied and reveal bonds with large ionic character for both phases. The B-Nb₂O₅ presented larger stiffness than T-Nb₂O₅, and the oxygen sites in the T-Nb₂O₅ are more compressible. The density of states comparison for both structures indicates that B-Nb₂O₅ has lower concentration of acid sites compared to T-Nb₂O₅. This result is consistent with the experimental observations that the concentration of Lewis acid sites decreases with the temperature.