skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry

Abstract

Bastnäsite, a fluoro-carbonate mineral, is the single largest mineral source of light rare earth elements (REE), La, Ce and Nd. Enhancing the efficiency of separation of the mineral from gangue through froth flotation is the first step towards meeting an ever increasing demand for REE. To design and evaluate collector molecules that selectively bind to bastnäsite, a fundamental understanding of the structure and surface properties of bastnäsite is essential. In our earlier work (J Phys Chem C, 2016, 120, 16767), we carried out an extensive study of the structure, surface stability and water adsorption energies of La-bastnäsite. Here in this work, we make a comparative study of the surface properties of Ce-bastnäsite, La-bastnäsite, and calcite using a combination of density functional theory (DFT) and water adsorption calorimetry. Spin polarized DFT+U calculations show that the exchange interaction between the electrons in Ce 4f orbitals is negligible and that these orbitals do not participate in bonding with the oxygen atom of the adsorbed water molecule. In agreement with calorimetry, DFT calculations predict larger surface energies and stronger water adsorption energies on Ce-bastnäsite than on La-bastnäsite. The order of stabilities for stoichiometric surfaces is as follows: [100] > [101] > [102] > [0001]more » > [112] > [104] and the most favorable adsorption sites for water molecules are the same as for La-bastnäsite. In agreement with water adsorption calorimetry, at low coverage water molecules are strongly stabilized via coordination to the surface Ce3+ ions, whereas at higher coverage they are adsorbed less strongly via hydrogen bonding interaction with the surface anions. Lastly, due to similar water adsorption energies on bastnäsite [101] and calcite [104] surfaces, the design of collector molecules that selectively bind to bastnäsite over calcite must exploit the structural differences in the predominantly exposed facets of these minerals.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [1];  [4];  [5];  [2]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  2. Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab. and NEAT ORU
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computer Science and Mathematics Division
  4. Rutgers Univ., Piscataway, NJ (United States). Dept. of Materials Science and Engineering
  5. OLI Systems, Inc., Cedar Knolls (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1408003
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 11; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Goverapet Srinivasan, Sriram, Shivaramaiah, Radha, Kent, Paul R. C., Stack, Andrew G., Riman, Richard, Anderko, Andre, Navrotsky, Alexandra, and Bryantsev, Vyacheslav S. A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry. United States: N. p., 2017. Web. doi:10.1039/C7CP00811B.
Goverapet Srinivasan, Sriram, Shivaramaiah, Radha, Kent, Paul R. C., Stack, Andrew G., Riman, Richard, Anderko, Andre, Navrotsky, Alexandra, & Bryantsev, Vyacheslav S. A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry. United States. doi:10.1039/C7CP00811B.
Goverapet Srinivasan, Sriram, Shivaramaiah, Radha, Kent, Paul R. C., Stack, Andrew G., Riman, Richard, Anderko, Andre, Navrotsky, Alexandra, and Bryantsev, Vyacheslav S. Fri . "A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry". United States. doi:10.1039/C7CP00811B. https://www.osti.gov/servlets/purl/1408003.
@article{osti_1408003,
title = {A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry},
author = {Goverapet Srinivasan, Sriram and Shivaramaiah, Radha and Kent, Paul R. C. and Stack, Andrew G. and Riman, Richard and Anderko, Andre and Navrotsky, Alexandra and Bryantsev, Vyacheslav S.},
abstractNote = {Bastnäsite, a fluoro-carbonate mineral, is the single largest mineral source of light rare earth elements (REE), La, Ce and Nd. Enhancing the efficiency of separation of the mineral from gangue through froth flotation is the first step towards meeting an ever increasing demand for REE. To design and evaluate collector molecules that selectively bind to bastnäsite, a fundamental understanding of the structure and surface properties of bastnäsite is essential. In our earlier work (J Phys Chem C, 2016, 120, 16767), we carried out an extensive study of the structure, surface stability and water adsorption energies of La-bastnäsite. Here in this work, we make a comparative study of the surface properties of Ce-bastnäsite, La-bastnäsite, and calcite using a combination of density functional theory (DFT) and water adsorption calorimetry. Spin polarized DFT+U calculations show that the exchange interaction between the electrons in Ce 4f orbitals is negligible and that these orbitals do not participate in bonding with the oxygen atom of the adsorbed water molecule. In agreement with calorimetry, DFT calculations predict larger surface energies and stronger water adsorption energies on Ce-bastnäsite than on La-bastnäsite. The order of stabilities for stoichiometric surfaces is as follows: [100] > [101] > [102] > [0001] > [112] > [104] and the most favorable adsorption sites for water molecules are the same as for La-bastnäsite. In agreement with water adsorption calorimetry, at low coverage water molecules are strongly stabilized via coordination to the surface Ce3+ ions, whereas at higher coverage they are adsorbed less strongly via hydrogen bonding interaction with the surface anions. Lastly, due to similar water adsorption energies on bastnäsite [101] and calcite [104] surfaces, the design of collector molecules that selectively bind to bastnäsite over calcite must exploit the structural differences in the predominantly exposed facets of these minerals.},
doi = {10.1039/C7CP00811B},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 11,
volume = 19,
place = {United States},
year = {2017},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The Mountain pass Rare-Earth Carbonatite and Associated Ultrapotassic Rocks, California
journal, August 2008


Convergence acceleration of iterative sequences. the case of scf iteration
journal, July 1980


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
  • DOI: 10.1063/1.4865107

A review of the beneficiation of rare earth element bearing minerals
journal, February 2013


Adsorption of oleate and octyl-hydroxamate on to rare-earths minerals
journal, March 1996


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
  • DOI: 10.1021/jp5016356

Charge Transport over the Defective CeO 2 (111) Surface
journal, August 2016


Molecular modeling and rational design of flotation reagents
journal, September 2003


Projector augmented-wave method
journal, December 1994


Low-temperature thermal expansion of LiH, MgO and CaO
journal, November 1968


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


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
  • DOI: 10.1021/jp309319j

Entropic contributions enhance polarity compensation for CeO2(100) surfaces
journal, November 2016

  • Capdevila-Cortada, Marçal; López, Núria
  • Nature Materials, Vol. 16, Issue 3
  • DOI: 10.1038/nmat4804

A new collector for rare earth mineral flotation
journal, December 1997


The role of inorganic and organic reagents in the flotation separation of rare-earth ores
journal, July 1991


Adsorption of hydroxamate collectors on semisoluble minerals Part II: Effect of temperature on adsorption
journal, January 1985


Utilisation of hydroxamates in minerals froth flotation
journal, January 1996


Crystal Structures, Surface Stability, and Water Adsorption Energies of La-Bastnäsite via Density Functional Theory and Experimental Studies
journal, July 2016

  • Srinivasan, Sriram Goverapet; Shivaramaiah, Radha; Kent, Paul R. C.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 30
  • DOI: 10.1021/acs.jpcc.6b04747

New software tools for the calculation and display of isolated and attached interfacial-energy minimizing particle shapes
journal, August 2012

  • Zucker, Rachel V.; Chatain, Dominique; Dahmen, Ulrich
  • Journal of Materials Science, Vol. 47, Issue 24
  • DOI: 10.1007/s10853-012-6739-x

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


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
  • DOI: 10.1021/jp806109y

Calibration of the DFT/GGA+U Method for Determination of Reduction Energies for Transition and Rare Earth Metal Oxides of Ti, V, Mo, and Ce
journal, June 2011

  • Lutfalla, Suzanne; Shapovalov, Vladimir; Bell, Alexis T.
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 7
  • DOI: 10.1021/ct200202g

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


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
  • DOI: 10.1021/acs.jpcc.5b04161

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Periodic boundary conditions in ab initio calculations
journal, February 1995


VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Surface chemistry aspects of bastnaesite flotation with octyl hydroxamate
journal, December 2014


Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008


Reply to “Comment on ‘Taming multiple valency with density functionals: A case study of defective ceria' ”
journal, December 2005


Energetics of oxide nanoparticles
journal, October 2009

  • Navrotsky, Alexandra
  • International Journal of Quantum Chemistry, Vol. 109, Issue 12
  • DOI: 10.1002/qua.21981

Surface Structure and Morphology of Calcium Carbonate Polymorphs Calcite, Aragonite, and Vaterite:  An Atomistic Approach
journal, April 1998

  • de Leeuw, Nora H.; Parker, Stephen C.
  • The Journal of Physical Chemistry B, Vol. 102, Issue 16
  • DOI: 10.1021/jp973210f

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Is the Calcite–Water Interface Understood? Direct Comparisons of Molecular Dynamics Simulations with Specular X-ray Reflectivity Data
journal, February 2013

  • Fenter, Paul; Kerisit, Sebastien; Raiteri, Paolo
  • The Journal of Physical Chemistry C, Vol. 117, Issue 10
  • DOI: 10.1021/jp310943s

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
  • DOI: 10.2138/am-2016-5565

Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992


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
  • DOI: 10.1021/es203518d

Material and Energy Requirement for Rare Earth Production
journal, August 2013


Ab initio calculation of the crystal structure of the lanthanide Ln2O3 sesquioxides
journal, March 2003


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
  • DOI: 10.1107/S0567740870003576

Method for locating low-energy solutions within DFT + U
journal, November 2010


Studies of the calcite cleavage surface for comparison with calculation
journal, December 1993


Ni on the CeO 2 (110) and (100) surfaces: adsorption vs. substitution effects on the electronic and geometric structures and oxygen vacancies
journal, January 2016

  • Li, W. Q.; Goverapet Srinivasan, S.; Salahub, D. R.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 16
  • DOI: 10.1039/C6CP00738D

The adsorption of hydroxamate on semi-soluble minerals. Part I: Adsorption on barite, Calcite and Bastnaesite
journal, December 1983


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
  • DOI: 10.1063/1.3382344

Spectroscopic investigation of the interaction of hydroxamate with bastnaesite (cerium) and rare earth oxides
journal, October 2012