Stabilization of MgAl2O4 spinel surfaces via doping
Abstract
Here, the surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. We report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl2O4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y3+, Gd3+, La3+) and one tetravalent dopant (Zr4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated bymore »
- Authors:
-
- Univ. of California, Davis, CA (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1256292
- Alternate Identifier(s):
- OSTI ID: 1359909
- Report Number(s):
- LA-UR-16-20588
Journal ID: ISSN 0039-6028
- Grant/Contract Number:
- AC52-06NA25396; BES ER46795; 2013LANL8400
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Surface Science
- Additional Journal Information:
- Journal Volume: 649; Journal Issue: C; Journal ID: ISSN 0039-6028
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Hasan, Md. M., Dholabhai, Pratik P., Castro, Ricardo H. R., and Uberuaga, Blas P. Stabilization of MgAl2O4 spinel surfaces via doping. United States: N. p., 2016.
Web. doi:10.1016/j.susc.2016.01.028.
Hasan, Md. M., Dholabhai, Pratik P., Castro, Ricardo H. R., & Uberuaga, Blas P. Stabilization of MgAl2O4 spinel surfaces via doping. United States. https://doi.org/10.1016/j.susc.2016.01.028
Hasan, Md. M., Dholabhai, Pratik P., Castro, Ricardo H. R., and Uberuaga, Blas P. Sat .
"Stabilization of MgAl2O4 spinel surfaces via doping". United States. https://doi.org/10.1016/j.susc.2016.01.028. https://www.osti.gov/servlets/purl/1256292.
@article{osti_1256292,
title = {Stabilization of MgAl2O4 spinel surfaces via doping},
author = {Hasan, Md. M. and Dholabhai, Pratik P. and Castro, Ricardo H. R. and Uberuaga, Blas P.},
abstractNote = {Here, the surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. We report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl2O4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y3+, Gd3+, La3+) and one tetravalent dopant (Zr4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.},
doi = {10.1016/j.susc.2016.01.028},
journal = {Surface Science},
number = C,
volume = 649,
place = {United States},
year = {Sat Feb 06 00:00:00 EST 2016},
month = {Sat Feb 06 00:00:00 EST 2016}
}
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Works referenced in this record:
Ultrathin metal films and particles on oxide surfaces: structural, electronic and chemisorptive properties
journal, January 1997
- Campbell, Charles T.
- Surface Science Reports, Vol. 27, Issue 1-3
Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering
journal, January 1998
- Renaud, G.
- Surface Science Reports, Vol. 32, Issue 1-2
Multiferroic BaTiO3-CoFe2O4 Nanostructures
journal, January 2004
- Zheng, H.
- Science, Vol. 303, Issue 5658
Recent Developments in Irradiation-Resistant Steels
journal, August 2008
- Odette, G. R.; Alinger, M. J.; Wirth, B. D.
- Annual Review of Materials Research, Vol. 38, Issue 1, p. 471-503
Massive Interfacial Reconstruction at Misfit Dislocations in Metal/Oxide Interfaces
journal, October 2014
- Choudhury, Samrat; Morgan, Dane; Uberuaga, Blas Pedro
- Scientific Reports, Vol. 4, Issue 1
On the equilibrium of heterogeneous substances
journal, December 1878
- Gibbs, J. W.
- American Journal of Science, Vol. s3-16, Issue 96
Reducing grain boundary, dislocation line and vacancy formation energies by solute segregation. I. Theoretical background
journal, September 2007
- Kirchheim, R.
- Acta Materialia, Vol. 55, Issue 15
Reducing grain boundary, dislocation line and vacancy formation energies by solute segregationII. Experimental evidence and consequences
journal, September 2007
- Kirchheim, R.
- Acta Materialia, Vol. 55, Issue 15
Alloy effects in nanostructures
journal, January 1993
- Weissmüller, J.
- Nanostructured Materials, Vol. 3, Issue 1-6
Surface Segregation on Manganese Doped Ceria Nanoparticles and Relationship with Nanostability
journal, December 2014
- Wu, Longjia; Dey, Sanchita; Gong, Mingming
- The Journal of Physical Chemistry C, Vol. 118, Issue 51
Thermodynamic Stability of SnO 2 Nanoparticles: The Role of Interface Energies and Dopants
journal, March 2015
- Chang, Chi-Hsiu; Gong, Mingming; Dey, Sanchita
- The Journal of Physical Chemistry C, Vol. 119, Issue 11
The role of sulfur in deactivation of Pt/MgAl2O4 for propane dehydrogenation
journal, April 1986
- Rennard, R.
- Journal of Catalysis, Vol. 98, Issue 2
Effect of the Synthesis Method of MgAl 2 O 4 and of Sn and Pb Addition to Platinum Catalysts on the Behavior in n -Butane Dehydrogenation
journal, March 2010
- Bocanegra, Sonia; Yañez, María Julia; Scelza, Osvaldo
- Industrial & Engineering Chemistry Research, Vol. 49, Issue 9
Stable platinum nanoparticles on specific MgAl2O4 spinel facets at high temperatures in oxidizing atmospheres
journal, September 2013
- Li, Wei-Zhen; Kovarik, Libor; Mei, Donghai
- Nature Communications, Vol. 4, Issue 1
Atomistic simulation of the surface structure of spinel
journal, January 1994
- Davies, Mark J.; Parker, Stephen C.; Watson, Graeme W.
- Journal of Materials Chemistry, Vol. 4, Issue 6
Atomistic Simulation of the Surface Energy of Spinel MgAl2O4
journal, August 2000
- Fang, Chang Ming; Parker, Stephen C.; With, Gijsbertus
- Journal of the American Ceramic Society, Vol. 83, Issue 8
Geometry of {001} Surfaces of Spinel (MgAl2O4): First-Principles Simulations and Experimental Measurements
journal, June 2005
- van der Laag, N. J.; Fang, C. M.; de With, G.
- Journal of the American Ceramic Society, Vol. 88, Issue 6
Structures of Fe 3 O 4 (111) surfaces observed by scanning tunneling microscopy
journal, April 1996
- Lennie, A. R.; Condon, N. G.; Leibsle, F. M.
- Physical Review B, Vol. 53, Issue 15
Periodic DFT and HR-STEM Studies of Surface Structure and Morphology of Cobalt Spinel Nanocrystals. Retrieving 3D Shapes from 2D Images
journal, March 2011
- Zasada, Filip; Piskorz, Witold; Stelmachowski, Paweł
- The Journal of Physical Chemistry C, Vol. 115, Issue 14
Configurational and energy study of the (100) and (110) surfaces of the MgAl 2 O 4 spinel by means of quantum mechanical and empirical techniques
journal, January 2014
- Massaro, Francesco Roberto; Bruno, Marco; Nestola, Fabrizio
- CrystEngComm, Vol. 16, Issue 39
Analysis and spectroscopy of rare earth doped magnesium aluminate spinel
journal, June 2005
- Perkins, J. M.; West, G. D.; Lewis, M. H.
- Advances in Applied Ceramics, Vol. 104, Issue 3
Characterisation of fine-grained oxide ceramics
journal, November 2004
- West, G. D.; Perkins, J. M.; Lewis, M. H.
- Journal of Materials Science, Vol. 39, Issue 22
Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995
- Plimpton, Steve
- Journal of Computational Physics, Vol. 117, Issue 1
Die Berechnung optischer und elektrostatischer Gitterpotentiale
journal, January 1921
- Ewald, P. P.
- Annalen der Physik, Vol. 369, Issue 3
Solution Mechanisms for Dopant Oxides in Yttria
journal, June 1999
- Busker, Gerdjan; Chroneos, Alex; Grimes, Robin W.
- Journal of the American Ceramic Society, Vol. 82, Issue 6
The stability of ionic crystal surfaces
journal, November 1979
- Tasker, P. W.
- Journal of Physics C: Solid State Physics, Vol. 12, Issue 22
The surface energies, surface tensions and surface structure of the alkali halide crystals
journal, February 1979
- Tasker, P. W.
- Philosophical Magazine A, Vol. 39, Issue 2
Dopant control over the crystal morphology of ceramic materials
journal, November 2007
- Alfredsson, Maria; Corà, Furio; Dobson, David P.
- Surface Science, Vol. 601, Issue 21
Stable Cation Inversion at the Surface
journal, July 2011
- Rasmussen, Morten K.; Foster, Adam S.; Hinnemann, Berit
- Physical Review Letters, Vol. 107, Issue 3
Dislocations at spinel surfaces
journal, June 2002
- Yanina, Svetlana V.; Barry Carter, C.
- Surface Science, Vol. 511, Issue 1-3
Terraces and ledges on (001) spinel surfaces
journal, July 2002
- Yanina, Svetlana V.; Barry Carter, C.
- Surface Science, Vol. 513, Issue 2, p. L402-L412
Nanophase Transition Metal Oxides Show Large Thermodynamically Driven Shifts in Oxidation-Reduction Equilibria
journal, October 2010
- Navrotsky, Alexandra; Ma, Chengcheng; Lilova, Kristina
- Science, Vol. 330, Issue 6001
Fracture of single crystal MgAl2O4
journal, January 1980
- Stewart, R. L.; Bradt, R. C.
- Journal of Materials Science, Vol. 15, Issue 1
Effective ionic radii in oxides and fluorides
journal, May 1969
- Shannon, R. D.; Prewitt, C. T.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 25, Issue 5
Revised values of effective ionic radii
journal, July 1970
- Shannon, R. D.; Prewitt, C. T.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 26, Issue 7
Structure and segregation of dopant–defect complexes at grain boundaries in nanocrystalline doped ceria
journal, January 2015
- Dholabhai, Pratik P.; Aguiar, Jeffery A.; Wu, Longjia
- Physical Chemistry Chemical Physics, Vol. 17, Issue 23
Mixing and non-stoichiometry in Fe–Ni–Cr–Zn–O spinel compounds: density functional theory calculations
journal, January 2013
- Andersson, David A.; Stanek, Christopher R.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 37
Non-stoichiometry in MgAl 2 O 4 spinel
journal, March 2010
- Murphy, S. T.; Gilbert, C. A.; Smith, R.
- Philosophical Magazine, Vol. 90, Issue 10
Defect processes in MgAl2O4 spinel
journal, June 2008
- Ball, J. A.; Murphy, S. T.; Grimes, R. W.
- Solid State Sciences, Vol. 10, Issue 6
Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach
journal, December 2014
- Lu, Jun; Zhan, Chun; Wu, Tianpin
- Nature Communications, Vol. 5, Issue 1
Potential models for ionic oxides
journal, February 1985
- Lewis, G. V.; Catlow, C. R. A.
- Journal of Physics C: Solid State Physics, Vol. 18, Issue 6
Segregation of Ba 2+ , Sr 2+ , Ce 4+ and Zr 4+ to UO 2 surfaces
journal, June 2004
- Stanek, C. R.; Bradford, M. R.; Grimes, R. W.
- Journal of Physics: Condensed Matter, Vol. 16, Issue 27
The role of charge and ionic radius on fission product segregation to a model UO 2 grain boundary
journal, April 2013
- Hong, Minki; Uberuaga, Blas P.; Phillpot, Simon R.
- Journal of Applied Physics, Vol. 113, Issue 13
Hartree-Fock calculations of electronic structure of (110)-surface of rutile TiO2: Comparison of single (2D) and periodic (3D) slab models
journal, January 2003
- Evarestov, R. A.; Bandura, A. V.
- International Journal of Quantum Chemistry, Vol. 96, Issue 3
Works referencing / citing this record:
Atomic-scale structure of misfit dislocations in CeO 2 /MgO heterostructures and thermodynamic stability of dopant–defect complexes at the heterointerface
journal, January 2019
- Dholabhai, Pratik P.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 37
Influence of Chemistry and Misfit Dislocation Structure on Dopant Segregation at Complex Oxide Heterointerfaces
journal, September 2018
- Dholabhai, Pratik P.; Martinez, Enrique; Uberuaga, Blas P.
- Advanced Theory and Simulations, Vol. 2, Issue 1
Alleviating oxygen evolution from Li-excess oxide materials through theory-guided surface protection
journal, November 2018
- Shin, Yongwoo; Kan, Wang Hay; Aykol, Muratahan
- Nature Communications, Vol. 9, Issue 1
Alleviating oxygen evolution from Li-excess oxide materials through theory-guided surface protection
journal, November 2018
- Shin, Yongwoo; Kan, Wang Hay; Aykol, Muratahan
- Nature Communications, Vol. 9, Issue 1