Solvation Properties of Silver and Copper Ions in a Room Temperature Ionic Liquid: A First-Principles Study

Pham, Tuan Anh; Horwood, Corie; Maiti, Amitesh; Peters, Vanessa; Bunn, Thomas; Stadermann, Michael

doi:10.1021/acs.jpcb.8b10559

Title: Solvation Properties of Silver and Copper Ions in a Room Temperature Ionic Liquid: A First-Principles Study

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Abstract

Understanding the behavior of metal ions in room temperature ionic liquids (ILs) is essential for predicting and optimizing performance for technologies like metal electrodeposition; however, many mechanistic details remain enigmatic, including the solvation properties of the ions in ILs and how they are governed by the intrinsic interaction between the ions and the liquid species. Here, we utilize first-principles molecular dynamics simulations to unravel and compare the key structural properties of Ag⁺ and Cu⁺ ions in a common room temperature IL, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. We find that, when compared to Cu⁺, the larger Ag⁺ shows a more disordered and flexible solvation structure with a more frequent exchange of the IL species between its solvation shells. In addition, our simulations reveal an interesting analog in the solvation behavior of the ions in the IL and aqueous environments, particularly in the effect of the ion electronic structures on their solvation properties. As a result, this work provides fundamental understanding of the intrinsic properties of the metal ions in the IL, while offering mechanistic understanding and strategy for future selection of ILs for metal electrodeposition processes.

Authors:

^[1]; Horwood, Corie ^[1]; Maiti, Amitesh ^[1]; Peters, Vanessa ^[1]; Bunn, Thomas ^[1]; Stadermann, Michael ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Publication Date:: Wed Nov 21 00:00:00 EST 2018

Research Org.:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1633523

Report Number(s):: LLNL-JRNL-778779
Journal ID: ISSN 1520-6106; 965870

Grant/Contract Number:: AC52-07NA27344

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 122; Journal Issue: 50; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; Oxygen; anions; metals; solvation; ions

Citation Formats


                    Pham, Tuan Anh, Horwood, Corie, Maiti, Amitesh, Peters, Vanessa, Bunn, Thomas, and Stadermann, Michael. Solvation Properties of Silver and Copper Ions in a Room Temperature Ionic Liquid: A First-Principles Study.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcb.8b10559.

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                    Pham, Tuan Anh, Horwood, Corie, Maiti, Amitesh, Peters, Vanessa, Bunn, Thomas, & Stadermann, Michael. Solvation Properties of Silver and Copper Ions in a Room Temperature Ionic Liquid: A First-Principles Study.  United States.  https://doi.org/10.1021/acs.jpcb.8b10559

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                    Pham, Tuan Anh, Horwood, Corie, Maiti, Amitesh, Peters, Vanessa, Bunn, Thomas, and Stadermann, Michael. Wed .  
"Solvation Properties of Silver and Copper Ions in a Room Temperature Ionic Liquid: A First-Principles Study".  United States.  https://doi.org/10.1021/acs.jpcb.8b10559.  https://www.osti.gov/servlets/purl/1633523.

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@article{osti_1633523,

  title        = {Solvation Properties of Silver and Copper Ions in a Room Temperature Ionic Liquid: A First-Principles Study},

  author       = {Pham, Tuan Anh and Horwood, Corie and Maiti, Amitesh and Peters, Vanessa and Bunn, Thomas and Stadermann, Michael},

  abstractNote = {Understanding the behavior of metal ions in room temperature ionic liquids (ILs) is essential for predicting and optimizing performance for technologies like metal electrodeposition; however, many mechanistic details remain enigmatic, including the solvation properties of the ions in ILs and how they are governed by the intrinsic interaction between the ions and the liquid species. Here, we utilize first-principles molecular dynamics simulations to unravel and compare the key structural properties of Ag+ and Cu+ ions in a common room temperature IL, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. We find that, when compared to Cu+, the larger Ag+ shows a more disordered and flexible solvation structure with a more frequent exchange of the IL species between its solvation shells. In addition, our simulations reveal an interesting analog in the solvation behavior of the ions in the IL and aqueous environments, particularly in the effect of the ion electronic structures on their solvation properties. As a result, this work provides fundamental understanding of the intrinsic properties of the metal ions in the IL, while offering mechanistic understanding and strategy for future selection of ILs for metal electrodeposition processes.},

  doi          = {10.1021/acs.jpcb.8b10559},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 50,

  volume       = 122,

  place        = {United States},

  year         = {Wed Nov 21 00:00:00 EST 2018},

  month        = {Wed Nov 21 00:00:00 EST 2018}

}

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