Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies
Abstract
Bastnasite is a fluoro-carbonate mineral that is the largest source of rare earth elements such as Y, La, and Ce. With increasing demand for REE in many emerging technologies, there is an urgent need for improving the efficiency of ore beneficiation by froth flotation. In order to design improved flotation agents that can selectively bind to the mineral surface, a fundamental understanding of the bulk and surface properties of bastnäsite is essential. Density functional theory calculations using the PBEsol exchange correlation functional and the DFT-D3 dispersion correction reveal that the most stable form of La-bastnäsite is isomorphic to the structure of Ce-bastnäsite belonging to the $$P\bar{62}c$$ space group, while the Inorganic Crystal Structure Database structure in the $$P\bar{62}m$$ space group is ca. 11.3 kJ/mol higher in energy per LaFCO3 formula unit. We report powder X-ray diffraction measurements on synthetic of La-bastnäsite to support these theoretical findings. Six different surfaces are studied by DFT, namely [$$10\bar{10}$$], [0001], [$$10\bar{11}$$], [$$10\bar{12}$$], [$$10\bar{14}$$] and [$$11\bar{22}$$]. Among these, the [$$10\bar{10}$$] surface is the most stable with a surface energy of 0.73 J/m2 in vacuum and 0.45 J/m2 in aqueous solution. We predicted the shape of a La-bastnäsite nanoparticle via thermodynamic Wulff construction to be a hexagonal prism with [$$10\bar{10}$$] and [0001] facets, chiseled at its ends by the [$$10\bar{11}$$] and [$$10\bar{12}$$] facets. The average surface energy of the nanoparticle in the gas phase is estimated to be 0.86 J/m2, in good agreement with a value of 1.11 J/m2 measured by calorimetry. The calculated adsorption energy of a water molecule varies widely with the surface plane and specific adsorption sites on a given surface. Moreover, the first layer of water molecules is predicted to adsorb strongly on the La-bastnäsite surface, in agreement with water adsorption calorimetry experiments. Our work provides an important step towards a detailed atomistic understanding of the bastnäsite water interface and designing collector molecules that can bind specifically to bastnäsite.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Univ. of California-Davis, Davis, CA (United States). Peter A. Rock Thermochemistry Lab. and NEAT ORU
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences and Computer Science and Mathematics Division
- State Univ. of New Jersey, Piscataway, NJ (United States). Dept. of Materials Science and Engineering, Rutgers
- OLI Systems, Inc., Cedar Knolls, NJ (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC)
- OSTI Identifier:
- 1286987
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231; AC0500OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 30; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Srinivasan, Sriram Goverapet, Shivaramaiah, Radha, Kent, Paul R. C., Stack, Andrew G., Navrotsky, Alexandra, Riman, Richard, Anderko, Andre, and Bryantsev, Vyacheslav S. Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies. United States: N. p., 2016.
Web. doi:10.1021/acs.jpcc.6b04747.
Srinivasan, Sriram Goverapet, Shivaramaiah, Radha, Kent, Paul R. C., Stack, Andrew G., Navrotsky, Alexandra, Riman, Richard, Anderko, Andre, & Bryantsev, Vyacheslav S. Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies. United States. https://doi.org/10.1021/acs.jpcc.6b04747
Srinivasan, Sriram Goverapet, Shivaramaiah, Radha, Kent, Paul R. C., Stack, Andrew G., Navrotsky, Alexandra, Riman, Richard, Anderko, Andre, and Bryantsev, Vyacheslav S. Mon .
"Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies". United States. https://doi.org/10.1021/acs.jpcc.6b04747. https://www.osti.gov/servlets/purl/1286987.
@article{osti_1286987,
title = {Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies},
author = {Srinivasan, Sriram Goverapet and Shivaramaiah, Radha and Kent, Paul R. C. and Stack, Andrew G. and Navrotsky, Alexandra and Riman, Richard and Anderko, Andre and Bryantsev, Vyacheslav S.},
abstractNote = {Bastnasite is a fluoro-carbonate mineral that is the largest source of rare earth elements such as Y, La, and Ce. With increasing demand for REE in many emerging technologies, there is an urgent need for improving the efficiency of ore beneficiation by froth flotation. In order to design improved flotation agents that can selectively bind to the mineral surface, a fundamental understanding of the bulk and surface properties of bastnäsite is essential. Density functional theory calculations using the PBEsol exchange correlation functional and the DFT-D3 dispersion correction reveal that the most stable form of La-bastnäsite is isomorphic to the structure of Ce-bastnäsite belonging to the $P\bar{62}c$ space group, while the Inorganic Crystal Structure Database structure in the $P\bar{62}m$ space group is ca. 11.3 kJ/mol higher in energy per LaFCO3 formula unit. We report powder X-ray diffraction measurements on synthetic of La-bastnäsite to support these theoretical findings. Six different surfaces are studied by DFT, namely [$10\bar{10}$], [0001], [$10\bar{11}$], [$10\bar{12}$], [$10\bar{14}$] and [$11\bar{22}$]. Among these, the [$10\bar{10}$] surface is the most stable with a surface energy of 0.73 J/m2 in vacuum and 0.45 J/m2 in aqueous solution. We predicted the shape of a La-bastnäsite nanoparticle via thermodynamic Wulff construction to be a hexagonal prism with [$10\bar{10}$] and [0001] facets, chiseled at its ends by the [$10\bar{11}$] and [$10\bar{12}$] facets. The average surface energy of the nanoparticle in the gas phase is estimated to be 0.86 J/m2, in good agreement with a value of 1.11 J/m2 measured by calorimetry. The calculated adsorption energy of a water molecule varies widely with the surface plane and specific adsorption sites on a given surface. Moreover, the first layer of water molecules is predicted to adsorb strongly on the La-bastnäsite surface, in agreement with water adsorption calorimetry experiments. Our work provides an important step towards a detailed atomistic understanding of the bastnäsite water interface and designing collector molecules that can bind specifically to bastnäsite.},
doi = {10.1021/acs.jpcc.6b04747},
journal = {Journal of Physical Chemistry. C},
number = 30,
volume = 120,
place = {United States},
year = {Mon Jul 11 00:00:00 EDT 2016},
month = {Mon Jul 11 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Rare earth metal recycling
conference, May 2011
- Meyer, Laura; Bras, Bert
- 2011 IEEE International Symposium on Sustainable Systems and Technology (ISSST), Proceedings of the 2011 IEEE International Symposium on Sustainable Systems and Technology
A review of the beneficiation of rare earth element bearing minerals
journal, February 2013
- Jordens, Adam; Cheng, Ying Ping; Waters, Kristian E.
- Minerals Engineering, Vol. 41
Evaluating Rare Earth Element Availability: A Case with Revolutionary Demand from Clean Technologies
journal, February 2012
- Alonso, Elisa; Sherman, Andrew M.; Wallington, Timothy J.
- Environmental Science & Technology, Vol. 46, Issue 6
The zero point of charge of calcite
journal, August 1967
- Somasundaran, P.; Agar, G. E.
- Journal of Colloid and Interface Science, Vol. 24, Issue 4
Electrokinetic study of the role of modifying agents in flotation of salt-type minerals
journal, May 1986
- Smith, R. W.; Shonnard, David
- AIChE Journal, Vol. 32, Issue 5
Adsorption of oleate and octyl-hydroxamate on to rare-earths minerals
journal, March 1996
- Pavez, O.; Brandao, P. R. G.; Peres, A. E. C.
- Minerals Engineering, Vol. 9, Issue 3
A new collector for rare earth mineral flotation
journal, December 1997
- Ren, J.; Lu, S.; Song, S.
- Minerals Engineering, Vol. 10, Issue 12
Selective flotation of bastnaesite from monazite in rare earth concentrates using potassium alum as depressant
journal, June 2000
- Ren, Jun; Song, Shaoxian; Lopez-Valdivieso, Alejandro
- International Journal of Mineral Processing, Vol. 59, Issue 3
Surface Chemical Characterization of Bastnaesite through Electrokinetics
journal, January 2015
- Pradip, ; Li, Charles C. H.; Fuerstenau, Douglas W.
- KONA Powder and Particle Journal, Vol. 32, Issue 0, p. 176-183
The adsorption of hydroxamate on semi-soluble minerals. Part I: Adsorption on barite, Calcite and Bastnaesite
journal, December 1983
- Pradip, ; Fuerstenau, D. W.
- Colloids and Surfaces, Vol. 8, Issue 2
Adsorption of hydroxamate collectors on semisoluble minerals Part II: Effect of temperature on adsorption
journal, January 1985
- Pradip, ; Fuerstenau, D. W.
- Colloids and Surfaces, Vol. 15
The role of inorganic and organic reagents in the flotation separation of rare-earth ores
journal, July 1991
- Pradip, ; Fuerstenau, D. W.
- International Journal of Mineral Processing, Vol. 32, Issue 1-2
Utilisation of hydroxamates in minerals froth flotation
journal, January 1996
- Assis, S. M.; Montenegro, L. C. M.; Peres, A. E. C.
- Minerals Engineering, Vol. 9, Issue 1
Spectroscopic investigation of the interaction of hydroxamate with bastnaesite (cerium) and rare earth oxides
journal, October 2012
- Cui, Jianlan; Hope, Gregory A.; Buckley, Alan N.
- Minerals Engineering, Vol. 36-38
Molecular modeling and rational design of flotation reagents
journal, September 2003
- Pradip, ; Rai, Beena
- International Journal of Mineral Processing, Vol. 72, Issue 1-4
Surface chemistry aspects of bastnaesite flotation with octyl hydroxamate
journal, December 2014
- Zhang, Xia; Du, Hao; Wang, Xuming
- International Journal of Mineral Processing, Vol. 133
IX. Über die Kristallstruktur von Bastnäsit
journal, October 1930
- Oftedal, Ivar
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 72, Issue 1-6
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Convergence acceleration of iterative sequences. the case of scf iteration
journal, July 1980
- Pulay, Péter
- Chemical Physics Letters, Vol. 73, Issue 2
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 78, Issue 7
Refinement of the trigonal crystal structure of lanthanum trifluoride with neutron diffraction data
journal, April 1985
- Zalkin, A.; Templeton, D. H.
- Acta Crystallographica Section B Structural Science, Vol. 41, Issue 2
Thermodynamics of bastnaesite: A major rare earth ore mineral
journal, May 2016
- Shivaramaiah, Radha; Anderko, Andre; Riman, Richard E.
- American Mineralogist, Vol. 101, Issue 5
Periodic boundary conditions in ab initio calculations
journal, February 1995
- Makov, G.; Payne, M. C.
- Physical Review B, Vol. 51, Issue 7
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992
- Neugebauer, Jörg; Scheffler, Matthias
- Physical Review B, Vol. 46, Issue 24
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
journal, February 2014
- Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
- The Journal of Chemical Physics, Vol. 140, Issue 8
Accuracy of exchange-correlation functionals and effect of solvation on the surface energy of copper
journal, June 2013
- Fishman, Matthew; Zhuang, Houlong L.; Mathew, Kiran
- Physical Review B, Vol. 87, Issue 24
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
EXPGUI , a graphical user interface for GSAS
journal, April 2001
- Toby, Brian H.
- Journal of Applied Crystallography, Vol. 34, Issue 2
Analysis of Anhydrous and Hydrated Surface Energies of gamma-Al 2 O 3 by Water Adsorption Microcalorimetry
journal, November 2012
- Castro, Ricardo H. R.; Quach, Dat V.
- The Journal of Physical Chemistry C, Vol. 116, Issue 46
Energetics of CO 2 and H 2 O Adsorption on Zinc Oxide
journal, July 2014
- Gouvêa, Douglas; Ushakov, Sergey V.; Navrotsky, Alexandra
- Langmuir, Vol. 30, Issue 30
Water Adsorption Microcalorimetry Model: Deciphering Surface Energies and Water Chemical Potentials of Nanocrystalline Oxides
journal, May 2014
- Drazin, John W.; Castro, Ricardo H. R.
- The Journal of Physical Chemistry C, Vol. 118, Issue 19
Polar oxide surfaces
journal, July 2000
- Noguera, Claudine
- Journal of Physics: Condensed Matter, Vol. 12, Issue 31
The stability of ionic crystal surfaces
journal, November 1979
- Tasker, P. W.
- Journal of Physics C: Solid State Physics, Vol. 12, Issue 22
Investigation of the Interaction of Water with the Calcite (10.4) Surface Using Ab Initio Simulation
journal, April 2009
- Lardge, J. S.; Duffy, D. M.; Gillan, M. J.
- The Journal of Physical Chemistry C, Vol. 113, Issue 17
Influence of HCOO – on Calcite Growth from First-Principles
journal, August 2015
- Addari, Danilo; Satta, Alessandra
- The Journal of Physical Chemistry C, Vol. 119, Issue 34
Works referencing / citing this record:
Jahn-Teller Distortion and Cation Ordering: The Crystal Structure of Paratooite-(La), a Superstructure of Carbocernaite
journal, June 2019
- Krivovichev, Sergey V.; Panikorovskii, Taras L.; Zolotarev, Andrey A.
- Minerals, Vol. 9, Issue 6
Collector Chemistry for Bastnaesite Flotation – Recent Developments
journal, August 2019
- Liu, Weiping; Wang, Xuming; Miller, Jan D.
- Mineral Processing and Extractive Metallurgy Review, Vol. 40, Issue 6