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Title: Hydration structure and water exchange kinetics at xenotime–water interfaces: implications for rare earth minerals separation

Abstract

Hydration of surface ions gives rise to structural heterogeneity and variable exchange kinetics of water at complex mineral–water interfaces. In this work, we employ ab initio molecular dynamics (AIMD) simulations and water adsorption calorimetry to examine the aqueous interfaces of xenotime, a phosphate mineral that contains predominantly Y3+ and heavy rare earth elements. Consistent with natural crystal morphology, xenotime is predicted to have a tetragonal prismatic shape, dominated by the {100} surface. Hydration of this surface induces multilayer interfacial water structures with distinct OH orientations, which agrees with recent crystal truncation rod measurements. The exchange kinetics between two adjacent water layers exhibits a wide range of underlying timescales (5–180 picoseconds), dictated by ion–water electrostatics. Adsorption of a bidentate hydroxamate ligand reveals that {100} xenotime surface can only accommodate monodentate coordination with water exchange kinetics strongly depending on specific ligand orientation, prompting us to reconsider traditional strategies for selective separation of rare-earth minerals.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of California, Davis, CA (United States)
  3. Univ. of California, Davis, CA (United States); Arizona State Univ., Tempe, AZ (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Manufacturing Office; USDOE Office of Science (SC)
OSTI Identifier:
1606748
Alternate Identifier(s):
OSTI ID: 1606459
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
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: 22; Journal Issue: 15; 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

Citation Formats

Roy, Santanu, Wu, Lili, Srinivasan, Sriram Goverapet, Stack, Andrew G., Navrotsky, Alexandra, and Bryantsev, Vyacheslav S. Hydration structure and water exchange kinetics at xenotime–water interfaces: implications for rare earth minerals separation. United States: N. p., 2020. Web. doi:10.1039/D0CP00087F.
Roy, Santanu, Wu, Lili, Srinivasan, Sriram Goverapet, Stack, Andrew G., Navrotsky, Alexandra, & Bryantsev, Vyacheslav S. Hydration structure and water exchange kinetics at xenotime–water interfaces: implications for rare earth minerals separation. United States. doi:https://doi.org/10.1039/D0CP00087F
Roy, Santanu, Wu, Lili, Srinivasan, Sriram Goverapet, Stack, Andrew G., Navrotsky, Alexandra, and Bryantsev, Vyacheslav S. Wed . "Hydration structure and water exchange kinetics at xenotime–water interfaces: implications for rare earth minerals separation". United States. doi:https://doi.org/10.1039/D0CP00087F. https://www.osti.gov/servlets/purl/1606748.
@article{osti_1606748,
title = {Hydration structure and water exchange kinetics at xenotime–water interfaces: implications for rare earth minerals separation},
author = {Roy, Santanu and Wu, Lili and Srinivasan, Sriram Goverapet and Stack, Andrew G. and Navrotsky, Alexandra and Bryantsev, Vyacheslav S.},
abstractNote = {Hydration of surface ions gives rise to structural heterogeneity and variable exchange kinetics of water at complex mineral–water interfaces. In this work, we employ ab initio molecular dynamics (AIMD) simulations and water adsorption calorimetry to examine the aqueous interfaces of xenotime, a phosphate mineral that contains predominantly Y3+ and heavy rare earth elements. Consistent with natural crystal morphology, xenotime is predicted to have a tetragonal prismatic shape, dominated by the {100} surface. Hydration of this surface induces multilayer interfacial water structures with distinct OH orientations, which agrees with recent crystal truncation rod measurements. The exchange kinetics between two adjacent water layers exhibits a wide range of underlying timescales (5–180 picoseconds), dictated by ion–water electrostatics. Adsorption of a bidentate hydroxamate ligand reveals that {100} xenotime surface can only accommodate monodentate coordination with water exchange kinetics strongly depending on specific ligand orientation, prompting us to reconsider traditional strategies for selective separation of rare-earth minerals.},
doi = {10.1039/D0CP00087F},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 15,
volume = 22,
place = {United States},
year = {2020},
month = {2}
}

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