Catalytic Properties of Selected Transition Metal Oxides—Computational Studies
387
V 2 O 3 (0001) and V 2 O 5 (001) surfaces was analysed by Göbke et al. [465] revealing
that a methoxy layer is formed after CH 3 OH adsorption and the abstracted hydrogen is stabilised on V=O groups with formation of hydroxy species. It was shown
that in case of V 2 O 3 (0001), H 2 O desorption produces additional defects effectively
doubling the methoxy coverage. For V 2 O 5 (001), the reactions for CH 3 OH and H 2 O
formation compete for the hydroxy species that stabilise the surface methoxy groups
by production of a hydrogen deficiency.
4 Conclusions
The issue of coordination environment in the solid-state world is dominated by
oxides. In the catalytic processes, the redox properties are defined mostly by the
presence and the environment of TM cations in various coordination, like in the bulk
or at the surface, owing to the wealth of their oxidation states, relatively close in
energy.
Even though the above discussed systems do not exhaust the wide variety of TM
in heterogeneous catalysis, this chapter aims to review the most successful computational methods used to describe their unique properties.
Since more involved methods (e.g. post-HF or GW methods and, for the larger
systems, even hybrid DFT functionals) are computationally very demanding, the
Hubbard DFT+U method is a good compromise nowadays. It should be, however,
carefully parameterised, taking into account the system and even the property to be
addressed.
Acknowledgements The present work was in part funded by the National Science Centre (grant
2016/23/B/ST4/00088). Part of the calculations were performed in the Cyfronet PL-Grid supercomputer centre in Kraków.
References
1. Hartwig JF (2010) Organotransition metal chemistry: from bonding to catalysis. University
Science Books, Sausalito
2. Fajardo J, Peters JC (2017) J Am Chem Soc 139(45):16105. https://doi.org/10.1021/jacs.
7b10204
3. Bethe H (1929) Annalen der Physik 395(2):133. https://doi.org/10.1002/andp.19293950202
4. Miessler GL, Fischer PJ, Tarr DA, (2014) Inorg Chem. Pearson
5. Barteau MA (1996) Chem Rev 96(4):1413. https://doi.org/10.1021/cr950222t
6. Hohenberg P, Kohn W (1964) Phys Rev 136(3B):B864 (1964). https://link.aps.org/doi/10.
1103/PhysRev.136.B864
7. Kohn W, Sham LJ (1965) Phys Rev 140(4A):A1133. https://doi.org/10.1103/PhysRev.140.
A1133. https://link.aps.org/doi/10.1103/PhysRev.140.A1133
8. Ceperley DM, Alder BJ (1980) Phys Rev Lett 45(7):566. http://escholarship.org/uc/item/
2d7023jm.pdf
387
V 2 O 3 (0001) and V 2 O 5 (001) surfaces was analysed by Göbke et al. [465] revealing
that a methoxy layer is formed after CH 3 OH adsorption and the abstracted hydrogen is stabilised on V=O groups with formation of hydroxy species. It was shown
that in case of V 2 O 3 (0001), H 2 O desorption produces additional defects effectively
doubling the methoxy coverage. For V 2 O 5 (001), the reactions for CH 3 OH and H 2 O
formation compete for the hydroxy species that stabilise the surface methoxy groups
by production of a hydrogen deficiency.
4 Conclusions
The issue of coordination environment in the solid-state world is dominated by
oxides. In the catalytic processes, the redox properties are defined mostly by the
presence and the environment of TM cations in various coordination, like in the bulk
or at the surface, owing to the wealth of their oxidation states, relatively close in
energy.
Even though the above discussed systems do not exhaust the wide variety of TM
in heterogeneous catalysis, this chapter aims to review the most successful computational methods used to describe their unique properties.
Since more involved methods (e.g. post-HF or GW methods and, for the larger
systems, even hybrid DFT functionals) are computationally very demanding, the
Hubbard DFT+U method is a good compromise nowadays. It should be, however,
carefully parameterised, taking into account the system and even the property to be
addressed.
Acknowledgements The present work was in part funded by the National Science Centre (grant
2016/23/B/ST4/00088). Part of the calculations were performed in the Cyfronet PL-Grid supercomputer centre in Kraków.
References
1. Hartwig JF (2010) Organotransition metal chemistry: from bonding to catalysis. University
Science Books, Sausalito
2. Fajardo J, Peters JC (2017) J Am Chem Soc 139(45):16105. https://doi.org/10.1021/jacs.
7b10204
3. Bethe H (1929) Annalen der Physik 395(2):133. https://doi.org/10.1002/andp.19293950202
4. Miessler GL, Fischer PJ, Tarr DA, (2014) Inorg Chem. Pearson
5. Barteau MA (1996) Chem Rev 96(4):1413. https://doi.org/10.1021/cr950222t
6. Hohenberg P, Kohn W (1964) Phys Rev 136(3B):B864 (1964). https://link.aps.org/doi/10.
1103/PhysRev.136.B864
7. Kohn W, Sham LJ (1965) Phys Rev 140(4A):A1133. https://doi.org/10.1103/PhysRev.140.
A1133. https://link.aps.org/doi/10.1103/PhysRev.140.A1133
8. Ceperley DM, Alder BJ (1980) Phys Rev Lett 45(7):566. http://escholarship.org/uc/item/
2d7023jm.pdf