I. Van Driessche

Aliovalent doping of CeO2: DFT study of oxidation state and vacancy effects

D.E.P. Vanpoucke, P. Bultinck, S. Cottenier, V. Van Speybroeck, I. Van Driessche
Journal of Materials Chemistry A
2 (3), 13723-13737
2014
A1

Abstract 

The modification of CeO2 properties by means of aliovalent doping is investigated within the ab initio density functional theory framework. Lattice parameters, dopant atomic radii, bulk moduli and thermal expansion coefficients of fluorite type Ce1-xMxO2-y (with M = Mg, V, Co, Cu, Zn, Nb, Ba, La, Sm, Gd, Yb, and Bi) are presented for 0.00 < x < 0.25. The relative stability of the doped systems is discussed, and the influence of oxygen vacancies is investigated. It is shown that oxygen vacancies tend to increase the lattice parameter, and strongly decrease the bulk modulus. Defect formation energies are correlated with calculated crystal radii and covalent radii of the dopants, and are shown to present no simple trend. The previously observed inverse relationship between the thermal expansion coefficient and the bulk modulus in group IV doped CeO2 [J. Am. Ceram. Soc., 2014, 97(1), 258] is shown to persist independent of the inclusion of charge compensating vacancies.

Open Access version available at UGent repository

DOI 

http://dx.doi.org/10.1039/c4ta02449d

Tetravalent doping of CeO2: The impact of valence electron character on group IV dopant influence

D.E.P. Vanpoucke, S. Cottenier, V. Van Speybroeck, I. Van Driessche, P. Bultinck
Journal of the American Ceramic Society
97 (1), 258-266
2014
A1

Abstract 

Fluorite CeO2 doped with group IV elements is studied within the DFT and DFT+U framework. Concentration dependent formation energies are calculated for Ce1−xZxO2 (Z= C, Si, Ge, Sn, Pb, Ti, Zr, Hf) with 0≤x≤0.25 and a roughly decreasing trend with ionic radius is observed. The influence of the valence and near valence electronic configuration is discussed, indicating the importance of filled d and f shells near the Fermi level for all properties investigated. A clearly different behavior of group IVa and IVb dopants is observed: the former are more suitable for surface modifications, the latter are more suitable for bulk modifications.\\ \indent For the entire set of group IV dopants, there exists an inverse relation between the change, due to doping, of the bulk modulus and the thermal expansion coefficients. Hirshfeld-I atomic charges show that charge transfer effects due to doping are limited to the nearest neighbor oxygen atoms.

DOI 

http://dx.doi.org/10.1111/jace.12650

Reply to ‘comment on “extending hirshfeld-I to bulk and periodic materials”’

D.E.P. Vanpoucke, I. Van Driessche, P. Bultinck
Journal of Computational Chemistry
Volume 34, Issue 5, pages 422-427
2013
A1
Published while none of the authors were employed at the CMM

Abstract 

The issues raised in the comment by Manz are addressed through the presentation of calculated atomic charges for NaF, NaCl, MgO, SrTiO3 , and La2Ce2O7 , using our previously presented method for calculating Hirshfeld-I charges in solids (Vanpoucke et al., J. Comput. Chem. doi: 10.1002/jcc.23088). It is shown that the use of pseudovalence charges is sufficient to retrieve the full all-electron Hirshfeld-I charges to good accuracy. Furthermore, we present timing results of different systems, containing up to over 200 atoms, underlining the relatively low cost for large systems. A number of theoretical issues are formulated, pointing out mainly that care must be taken when deriving new atoms in molecules methods based on “expectations” for atomic charges.

Open Access version available at UGent repository

DOI 

http://dx.doi.org/10.1002/jcc.23193

Extending Hirshfeld-I to bulk and periodic materials

D.E.P. Vanpoucke, P. Bultinck, I. Van Driessche
Journal of Computational Chemistry
Volume 34, Issue 5, pages 405-417
2013
A1
Published while none of the authors were employed at the CMM

Abstract 

In this work, a method is described to extend the iterative Hirshfeld-I method, generally used for molecules, to periodic systems. The implementation makes use of precalculated pseudopotential-based electron density distributions, and it is shown that high-quality results are obtained for both molecules and solids, such as ceria, diamond, and graphite. The use of grids containing (precalculated) electron densities makes the implementation independent of the solid state or quantum chemical code used for studying the system. The extension described here allows for easy calculation of atomic charges and charge transfer in periodic and bulk systems. The conceptual issue of obtaining reference densities for anions is discussed, and the delocalization problem for anionic reference densities originating from the use of a plane wave basis set is identified and handled.

Open Access version available at UGent repository

DOI 

http://dx.doi.org/10.1002/jcc.23088

Quantification of silanol sites for the most common mesoporous ordered silicas and organosilicas: total versus accessible silanols

M. Ide, M. El-Roz, E. De Canck, A. Vicente, T. Planckaert, T. Bogaerts, I. Van Driessche, F. Lynen, V. Van Speybroeck, F. Thibault-Starzyk, P. Van der Voort
Physical Chemistry Chemical Physics (PCCP)
15, 642-650
2013
A1

Abstract 

IR and NMR spectroscopy were used to determine the silanol content in the most common mesoporous ordered silicas: MCM-41, MCM-48, SBA-15 and SBA-16. In addition, a spray dried MCM-41 and an ethene bridged PMO are investigated. The results are compared with a commercial chromatographic silica (Nucleosil). The complete distribution of surface and bulk silanols, and of isolated, geminal and vicinal silanols for all these materials is presented. A distinction is made between the total silanol number and the reachable or surface silanol content. The latter is determined by controlled reactions with simple silanes. All mesoporous ordered silicas, and especially the thick walled SBA-type materials and the PMO contain a surprisingly high amount of total silanol sites, albeit that up to 90% if these silanols are buried inside the walls and are not reachable for small silanes.

DOI 

http://dx.doi.org/10.1039/C2CP42811C

Tuning of CeO2 buffer layers for coated superconductors through doping

D.E.P. Vanpoucke, S. Cottenier, V. Van Speybroeck, P. Bultinck, I. Van Driessche
Applied Surface Science
260, 32-35
2012
A1

Abstract 

The appearance of microcracks in cerium oxide (CeO 2) buffer layers, as used in buffer layer architectures for coated superconductors, indicates the presence of stress between this buffer layer and the substrate. This stress can originate from the differences in thermal expansion or differences in lattice parameters between the CeO 2 buffer layer and the substrate. In this article, we study, by means of ab initio density functional theory calculations, the influence of group IV doping elements on the lattice parameter and bulk modulus of CeO 2. Vegard's law behavior is found for the lattice parameter in systems without oxygen vacancies, and the Shannon crystal radii for the doping elements are retrieved from the lattice expansions. We show that the lattice parameter of the doped CeO 2 can be matched to that of the La 2Zr 2O 7 coated NiW substrate substrate for dopant concentrations of about 5%, and that bulk modulus matching is either not possible or would require extreme doping concentrations. [All rights reserved Elsevier].

Open Access version available at UGent repository

DOI 

http://dx.doi.org/10.1016/j.apsusc.2012.01.032

Synthesis, characterization and sorption properties of NH2-MIL-47

K. Leus, S. Couck, M. Vandichel, G. Vanhaelewyn, Y-Y Liu, G.B. Marin, I. Van Driessche, D. Depla, M. Waroquier, V. Van Speybroeck, J.F.M. Denayer, P. Van der Voort
Physical Chemistry Chemical Physics (PCCP)
14, 15562–15570
2012
A1

Abstract 

An amino functionalized vanadium-containing Metal Organic Framework, NH2-MIL-47 has been synthesized by a hydrothermal reaction in an autoclave. Alternatively, a synthesis route via microwave enhanced irradiation has been optimized to accelerate the synthesis. The NH2-MIL-47 exhibits the same topology as MIL-47, in which the V center is octahedrally coordinated. After an exchange procedure in DMF the V+III center is oxidized to V+IV, which is confirmed by EPR and XPS measurements. The CO2 and CH4 adsorption properties have been evaluated and compared to MIL-47, showing that both MOFs have an almost similar adsorption capacity and affinity for CO2. DFT- based molecular modeling calculations were performed to obtain more insight into the adsorption positions for CO2 in NH2-MIL-47. Furthermore our calculated adsorption enthalpies agree well with the experimental values.

DOI 

http://dx.doi.org/10.1039/C2CP42137B

Density functional theory study of La2Ce2O7: Disordered fluorite versus pyrochlore structure

D.E.P. Vanpoucke, P. Bultinck, S. Cottenier, V. Van Speybroeck, I. Van Driessche
Physical Review B
84, 054110
2011
A1

Abstract 

The crystal structure of lanthanum cerium oxide (La2Ce2O7) is investigated using ab initio density functional theory calculations. The relative stability of fluorite- and pyrochlorelike structures is studied through comparison of their formation energies. These formation energies show the pyrochlore structure to be favored over the fluorite structure, apparently contradicting the conclusions based on experimental neutron and x-ray diffraction (XRD). By calculating and comparing XRD spectra for a set of differently ordered and random structures, we show that the pyrochlore structure is consistent with diffraction experiments. For these reasons, we suggest the pyrochlore structure as the ground-state crystal structure for La2Ce2O7. © 2011 American Physical Society

DOI 

http://dx.doi.org/10.1103/PhysRevB.84.054110

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