Numerical Study of the Zirconium Oxide System

Abstract

Zirconium dioxide is an important ceramic material. In this study, we report on a study of the zirconium oxide system. Based on Density Functional Theory (DFT) at B3LYP/SVP calculation level, we predict that geometries and energies of compounds will result from reactions of the ZrO₂ system. Enthalpies, , of a series of stable molecules and radicals were calculated using DFT calculations, while the Density Functional calculations were combined with isodesmic reaction analysis. Bond energies were estimated as well. We found that generally the Zr—X bonds are stronger than C—X bonds (X = O, C). Zr—OC bonds are stronger by some 50 kcal mol⁻¹ than C—OC bonds and ZrO—C bonds stronger by some 20 kcal mol ⁻¹ than CO—C bonds. ZrOZr—OX (X = OC, OCC, OC(=O)C) are also stronger by 40 kcal mol ⁻¹ than the COC—OX species and ZrOZr—OH bonds are stronger than COC—OH by 40 kcal mol ⁻¹. Kinetic calculations on zirconium oxide species are reported in this work. The final investigation of the present work was to optimize the sorption properties of small organic molecules on nano-ZrO₂.

Keywords:

• ZrO₂
• Thermochemistry
• Bond energies

ACKNOWLEDGMENTS

The authors are grateful to The “Deutsche Forschungsgemeinschaft” which supported this work. This study is a part of the “Schwerpunktprogramm 1155: Molekulare Modellierung und Simulation in der Verfahrenstechnik.”