Solubility model of metal complex in ionic liquids from first principle calculations

Karmakar, Anwesa; Mukundan, Rangachary; Yang, Ping; Batista, Enrique R.

doi:10.1039/C9RA04042K

Title: Solubility model of metal complex in ionic liquids from first principle calculations

Journal Article · 12 June 2019 · RSC Advances

DOI: https://doi.org/10.1039/C9RA04042K · OSTI ID:1525895

^[1]; Mukundan, Rangachary ^[1];

^[1];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

A predictive model based on first principles calculations has been proposed to study the solid–liquid equilibria comprising of metal complexes and ionic liquids. The model is based on first principle COSMO calculation followed by post statistical thermodynamical treatment of self-consistent properties of solute and solvent molecules. The metal complex and ionic liquid have been treated as a simple binary mixture. The ionic liquid has been treated here as a single intact molecule. The experimentally observed dual-solute relationship between the ionic liquid and redox active species in presence of a third organic solvent has been established using our model in this work. Within the model, the dual-solute relationship appeared as a simple Gibbs–Duhem relationship between these two species at ambient condition. The dual-solute relationship between the metal complex (V(acac)₃, Cr(acac)₃ and Mn(acac)₃) and ionic liquid ([Tea][BF₄]) has been validated by calculating the Gibbs–Duhem relationship, x_solute vs. x_solvent(IL) and 1/γ_solute vs. x_solvent(IL) plots. The present model has been applied to a set of ionic liquids, metal complexes and organic solvent (acetonitrile) for which experimental study has been done. The solvation mechanism of the metal complexes in those ionic liquids was obtained using the model. According to our findings, the ionic liquid containing imidazolium cation and [NTf₂]^- anion is appeared as a suitable solvent for the non-aqueous redox flow cell. We have compared our results with the already reported experimental results where they were available for the non-aqueous solvents.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE; LANL Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1525895

Alternate ID(s):: OSTI ID: 1542849

Report Number(s):: LA-UR-19-21357

Journal Information:: RSC Advances, Vol. 9, Issue 32; ISSN 2046-2069

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 19 works

Citation information provided by
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References (48)

Prospects of applying ionic liquids and deep eutectic solvents for renewable energy storage by means of redox flow batteries Chakrabarti, Mohammed Harun; Mjalli, Farouq Sabri; AlNashef, Inas Muen Renewable and Sustainable Energy Reviews, Vol. 30 https://doi.org/10.1016/j.rser.2013.10.004	journal	February 2014
Electrochemical Reaction of Tris(1,10-phenanthroline)iron Complexes in Some Amide-Type Ionic Liquids Katayama, Yasushi; Yoshihara, Mami; Miura, Takashi Journal of The Electrochemical Society, Vol. 162, Issue 8 https://doi.org/10.1149/2.0091508jes	journal	January 2015
Estimating Solid–Liquid Phase Change Enthalpies and Entropies Chickos, James S.; Acree, William E.; Liebman, Joel F. Journal of Physical and Chemical Reference Data, Vol. 28, Issue 6 https://doi.org/10.1063/1.556045	journal	November 1999
Electrode Kinetics of Some Iron Complexes in an Imide-Type Room-Temperature Ionic Liquid Tachikawa, Naoki; Katayama, Yasushi; Miura, Takashi Journal of The Electrochemical Society, Vol. 154, Issue 11 https://doi.org/10.1149/1.2777110	journal	January 2007
COSMOSPACE: Alternative to conventional activity-coefficient models Klamt, Andreas; Krooshof, Gerard J. P.; Taylor, Ross AIChE Journal, Vol. 48, Issue 10 https://doi.org/10.1002/aic.690481023	journal	October 2002
1,3-Dioxolane, tetrahydrofuran, acetylacetone and dimethyl sulfoxide as solvents for non-aqueous vanadium acetylacetonate redox-flow-batteries Herr, T.; Noack, J.; Fischer, P. Electrochimica Acta, Vol. 113 https://doi.org/10.1016/j.electacta.2013.09.055	journal	December 2013
Estimation of Pure-Component Properties from Group-Contributions Joback, K. G.; Reid, R. C. Chemical Engineering Communications, Vol. 57, Issue 1-6 https://doi.org/10.1080/00986448708960487	journal	July 1987
Predicting the potentials, solubilities and stabilities of metal-acetylacetonates for non-aqueous redox flow batteries using density functional theory calculations Kucharyson, J. F.; Cheng, L.; Tung, S. O. Journal of Materials Chemistry A, Vol. 5, Issue 26 https://doi.org/10.1039/C7TA01285C	journal	January 2017
Improvements of COSMO-SAC for vapor–liquid and liquid–liquid equilibrium predictions Hsieh, Chieh-Ming; Sandler, Stanley I.; Lin, Shiang-Tai Fluid Phase Equilibria, Vol. 297, Issue 1 https://doi.org/10.1016/j.fluid.2010.06.011	journal	October 2010
Solvents and supporting electrolytes for vanadium acetylacetonate flow batteries Shinkle, Aaron A.; Pomaville, Timothy J.; Sleightholme, Alice E. S. Journal of Power Sources, Vol. 248 https://doi.org/10.1016/j.jpowsour.2013.10.034	journal	February 2014
Systematic selection of solvent mixtures for non-aqueous redox flow batteries – vanadium acetylacetonate as a model system Bamgbopa, Musbaudeen O.; Pour, Nir; Shao-Horn, Yang Electrochimica Acta, Vol. 223 https://doi.org/10.1016/j.electacta.2016.12.014	journal	January 2017
Refinement and Parametrization of COSMO-RS Klamt, Andreas; Jonas, Volker; Bürger, Thorsten The Journal of Physical Chemistry A, Vol. 102, Issue 26 https://doi.org/10.1021/jp980017s	journal	June 1998
Electrochemical behavior of several iron complexes in hydrophobic room-temperature ionic liquids Yamagata, Masaki; Tachikawa, Naoki; Katayama, Yasushi Electrochimica Acta, Vol. 52, Issue 9 https://doi.org/10.1016/j.electacta.2006.10.008	journal	February 2007
Room temperature ionic liquid electrolytes for redox flow batteries Ejigu, Andinet; Greatorex-Davies, Peter A.; Walsh, Darren A. Electrochemistry Communications, Vol. 54 https://doi.org/10.1016/j.elecom.2015.01.016	journal	May 2015
DSC determination of the fusion and sublimation enthalpy of tris(2,4-pentanedionato)chromium(III) and iron(III) Murray, J. P.; Hill, J. O. Thermochimica Acta, Vol. 72, Issue 3 https://doi.org/10.1016/0040-6031(84)85092-3	journal	January 1984
Gibbs-duhem-margules laws Gokcen, N. A. Journal of Phase Equilibria, Vol. 17, Issue 1 https://doi.org/10.1007/BF02648369	journal	January 1996
Electrode kinetics in non-aqueous vanadium acetylacetonate redox flow batteries Shinkle, Aaron A.; Sleightholme, Alice E. S.; Thompson, Levi T. Journal of Applied Electrochemistry, Vol. 41, Issue 10 https://doi.org/10.1007/s10800-011-0314-z	journal	June 2011
Is the Enthalpy of Fusion of Tris(acetylacetonato)metal(III) Complexes Affected by Their Potential Energy in the Crystal State? Sabolović, Jasmina; Mrak, Željko; Koštrun, Sanja Inorganic Chemistry, Vol. 43, Issue 26 https://doi.org/10.1021/ic048900u	journal	December 2004
Electrode Kinetics of Ferrocenium/Ferrocene in Some Amide-Based Room-Temperature Ionic Liquids Tachikawa, Naoki; Katayama, Yasushi; Miura, Takashi Electrochemical and Solid-State Letters, Vol. 12, Issue 11 https://doi.org/10.1149/1.3213542	journal	January 2009
An Improvement to COSMO-SAC for Predicting Thermodynamic Properties Xiong, Ruichang; Sandler, Stanley I.; Burnett, Russell I. Industrial & Engineering Chemistry Research, Vol. 53, Issue 19 https://doi.org/10.1021/ie404410v	journal	April 2014
A review of current developments in non-aqueous redox flow batteries: characterization of their membranes for design perspective Shin, Sung-Hee; Yun, Sung-Hyun; Moon, Seung-Hyeon RSC Advances, Vol. 3, Issue 24, p. 9095-9116 https://doi.org/10.1039/c3ra00115f	journal	January 2013
Thermal properties of transition metal compounds Melia, T. P.; Merrifield, R. Journal of Inorganic and Nuclear Chemistry, Vol. 32, Issue 8 https://doi.org/10.1016/0022-1902(70)80304-9	journal	August 1970
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient Klamt, A.; Schüürmann, G. J. Chem. Soc., Perkin Trans. 2, Issue 5 https://doi.org/10.1039/P29930000799	journal	January 1993
Thermal and kinetic studies of some complexes of 2,4-pentanedione Beech, Graham; Lintonbon, Roger M. Thermochimica Acta, Vol. 3, Issue 2 https://doi.org/10.1016/0040-6031(71)80003-5	journal	December 1971
Electrodeposition of Cobalt from an Imide-Type Room-Temperature Ionic Liquid Katayama, Yasushi; Fukui, Ryuta; Miura, Takashi Journal of The Electrochemical Society, Vol. 154, Issue 10 https://doi.org/10.1149/1.2768298	journal	January 2007
Metal acetylacetonate complexes for high energy density non-aqueous redox flow batteries Suttil, J. A.; Kucharyson, J. F.; Escalante-Garcia, I. L. Journal of Materials Chemistry A, Vol. 3, Issue 15 https://doi.org/10.1039/C4TA06622G	journal	January 2015
Cyclic Voltammetry of Metallic Acetylacetonate Salts in Quaternary Ammonium and Phosphonium Based Deep Eutectic Solvents Chakrabarti, Mohammed Harun; Brandon, Nigel P.; Mjalli, Farouq S. Journal of Solution Chemistry, Vol. 42, Issue 12 https://doi.org/10.1007/s10953-013-0111-x	journal	November 2013
On the origin of ionicity in ionic liquids. Ion pairing versus charge transfer Hollóczki, Oldamur; Malberg, Friedrich; Welton, Tom Phys. Chem. Chem. Phys., Vol. 16, Issue 32 https://doi.org/10.1039/C4CP01177E	journal	January 2014
Tetrabutylammonium hexafluorophosphate and 1-ethyl-3-methyl imidazolium hexafluorophosphate ionic liquids as supporting electrolytes for non-aqueous vanadium redox flow batteries Zhang, Dapeng; Liu, Qinghua; Shi, Xiaosong Journal of Power Sources, Vol. 203 https://doi.org/10.1016/j.jpowsour.2011.10.136	journal	April 2012
Non-aqueous manganese acetylacetonate electrolyte for redox flow batteries Sleightholme, Alice E. S.; Shinkle, Aaron A.; Liu, Qinghua Journal of Power Sources, Vol. 196, Issue 13, p. 5742-5745 https://doi.org/10.1016/j.jpowsour.2011.02.020	journal	July 2011
Redox Reaction of Tris(acetylacetonato)iron(III) Complex in an Amide-type Ionic Liquid Tachikawa, Naoki; Haruyama, Ryo; Yoshii, Kazuki Electrochemistry, Vol. 86, Issue 2 https://doi.org/10.5796/electrochemistry.17-00080	journal	January 2018
An historic and scientific study of the properties of metal(III) tris-acetylacetonates Arslan, Evrim; Lalancette, Roger A.; Bernal, Ivan Structural Chemistry, Vol. 28, Issue 1 https://doi.org/10.1007/s11224-016-0864-0	journal	November 2016
Performance of a Non-Aqueous Vanadium Acetylacetonate Prototype Redox Flow Battery: Examination of Separators and Capacity Decay Escalante-García, Ismailia L.; Wainright, Jesse S.; Thompson, Levi T. Journal of The Electrochemical Society, Vol. 162, Issue 3 https://doi.org/10.1149/2.0471503jes	journal	December 2014
Nonaqueous redox-flow batteries: organic solvents, supporting electrolytes, and redox pairs Gong, Ke; Fang, Qianrong; Gu, Shuang Energy & Environmental Science, Vol. 8, Issue 12, p. 3515-3530 https://doi.org/10.1039/C5EE02341F	journal	January 2015
DSC and vapour pressure investigation of some β-diketonates Lazarev, V. B.; Greenberg, J. H.; Ozerova, Z. P. Journal of Thermal Analysis, Vol. 33, Issue 3 https://doi.org/10.1007/BF02138589	journal	September 1988
Liquid—liquid phase splitting—I analytical models for critical mixing and azeotropy Wisniak, Jaime Chemical Engineering Science, Vol. 38, Issue 6 https://doi.org/10.1016/0009-2509(83)80017-7	journal	January 1983
The COSMO and COSMO-RS solvation models: The COSMO and COSMO-RS solvation models Klamt, Andreas Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 5 https://doi.org/10.1002/wcms.56	journal	April 2011
Effects of the Interaction between Ionic Liquids and Redox Couples on Their Reaction Entropies Yamato, Yoshinori; Katayama, Yasushi; Miura, Takashi Journal of The Electrochemical Society, Vol. 160, Issue 6 https://doi.org/10.1149/2.055306jes	journal	January 2013
Total phase change entropies and enthalpies Chickos, James S.; Acree, William E. Thermochimica Acta, Vol. 395, Issue 1-2 https://doi.org/10.1016/S0040-6031(02)00213-7	journal	January 2002
Non-aqueous vanadium acetylacetonate electrolyte for redox flow batteries Liu, Qinghua; Sleightholme, Alice E. S.; Shinkle, Aaron A. Electrochemistry Communications, Vol. 11, Issue 12, p. 2312-2315 https://doi.org/10.1016/j.elecom.2009.10.006	journal	December 2009
Degradation mechanisms in the non-aqueous vanadium acetylacetonate redox flow battery Shinkle, Aaron A.; Sleightholme, Alice E. S.; Griffith, Lucas D. Journal of Power Sources, Vol. 206 https://doi.org/10.1016/j.jpowsour.2010.12.096	journal	May 2012
The entropy of high polymer solutions. Generalization of formulae Staverman, A. J. Recueil des Travaux Chimiques des Pays-Bas, Vol. 69, Issue 2 https://doi.org/10.1002/recl.19500690203	journal	January 1950
COSMO-RS: a novel and efficient method for the a priori prediction of thermophysical data of liquids Klamt, Andreas; Eckert, Frank Fluid Phase Equilibria, Vol. 172, Issue 1 https://doi.org/10.1016/S0378-3812(00)00357-5	journal	July 2000
Thermal properties of transition metal compounds Melia, T. P.; Merrifield, R. Journal of Inorganic and Nuclear Chemistry, Vol. 32, Issue 6 https://doi.org/10.1016/0022-1902(70)80596-6	journal	June 1970
Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays Smolentsev, Grigory; Milne, Christopher J.; Guda, Alexander Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15998-z	journal	May 2020
Electrodeposition of Cobalt from an Imide-Type Room-Temperature Ionic Liquid Katayama, Yasushi; Fukui, Ryuta; Miura, Takashi ECS Transactions, Vol. 3, Issue 35 https://doi.org/10.1149/1.2798672	journal	October 2006
Electrochemical Reaction of Tris(1,10-phenanthroline)Iron Complexes in Some Amide-Type Ionic Liquids Katayama, Y.; Yoshihara, M.; Miura, T. ECS Transactions, Vol. 64, Issue 4 https://doi.org/10.1149/06404.0109ecst	journal	August 2014
Electrode Kinetics of Some Iron Complexes in an Imide-type Room-temperature Ionic Liquid Tachikawa, Naoki; Katayama, Yasushi; Miura, Takashi ECS Transactions, Vol. 3, Issue 35 https://doi.org/10.1149/1.2798699	journal	October 2007

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Title: Solubility model of metal complex in ionic liquids from first principle calculations

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