Spectroscopic Insight on Neodymium Solvation in Lithium Borohydride-Supported Electrolyte

Atifi, Abderrahman; Pilgrim, Corey David; Zarzana, Christopher A.

doi:10.1021/acs.jpcb.4c06917

Title: Spectroscopic Insight on Neodymium Solvation in Lithium Borohydride-Supported Electrolyte

Journal Article · 11 December 2024 · Journal of Physical Chemistry. B

DOI: https://doi.org/10.1021/acs.jpcb.4c06917 · OSTI ID:2503501

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Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Borohydride-based electrolytes have recently emerged as promising media for the electrodeposition of electropositive metals, including rare earth (RE) elements. While the presence of supporting alkali metal cations and RE counteranions provides essential electrochemical conductivity for achieving fast metal electrodeposition, interactions between the host ligand and solvated neodymium (Nd) complexes remain unclear. This study provides insights into the coordination structure of a concentrated and directly solvated Nd salt in a lithium borohydride-supported electrolyte. Our spectroscopic results indicate that the RE coordination environment is significantly influenced by the solvation mechanism, which can vary between metathesis and complexation pathways, primarily dictated by stoichiometric factors. Under dilute conditions, nearly complete metathesis of anions leads to a high coordination number for the host ligand (borohydride), consistent with the previously reported solvated Nd speciation in chlorine-free electrolytes. In contrast, concentrated dissolution of the Nd salt in the supported electrolyte is dominated by a complexation pathway featuring a Li-ion-paired complex with a low coordination number of the host ligand. Density functional theory (DFT) calculations indicated that the observed blue shift in the borohydride vibration was the result of an increase in electron density drawn into the terminal B–H interbond region from the hydride as the coordination changed from Li to Nd. In conjunction with DFT results, vibrational analyses allowed correlation of the experimental shifts associated with changes in Nd ligation and coordination spheres, further consolidating the prevalence of highly chloride-coordinated species under concentrated conditions. In conclusion, the outcomes of this work illuminate the distinctive and heterogeneous coordination structures that the electroactive RE species can adopt at high concentrations in lithium borohydride-supported electrolytes, as a key step to comprehend the reported metal electrodeposition performance in these media.

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Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 2503501

Report Number(s):: INL/JOU--24-81424-Rev000

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 51 Vol. 128; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Best‐Practice DFT Protocols for Basic Molecular Computational Chemistry** Bursch, Markus; Mewes, Jan‐Michael; Hansen, Andreas Angewandte Chemie, Vol. 134, Issue 42 https://doi.org/10.1002/ange.202205735	journal	September 2022
Multiwfn: A multifunctional wavefunction analyzer Lu, Tian; Chen, Feiwu Journal of Computational Chemistry, Vol. 33, Issue 5 https://doi.org/10.1002/jcc.22885	journal	December 2011
Progress in preparation of rare earth metals and alloys by electrodeposition in molten salts Han, Wei; Li, Mei; Zhang, Mi-Lin Rare Metals, Vol. 35, Issue 11 https://doi.org/10.1007/s12598-016-0798-0	journal	October 2016
Borohydride complexes of rare earths, and their applications in various organic transformations Visseaux, Marc; Bonnet, Fanny Coordination Chemistry Reviews, Vol. 255, Issue 3-4 https://doi.org/10.1016/j.ccr.2010.09.016	journal	February 2011
Attempts to the electrodeposition of Nd from ionic liquids at elevated temperatures Kondo, Hitomi; Matsumiya, Masahiko; Tsunashima, Katsuhiko Electrochimica Acta, Vol. 66 https://doi.org/10.1016/j.electacta.2012.01.101	journal	April 2012
Electrochemical analysis of diffusion behavior and nucleation mechanism for Dy(II) and Dy(III) in phosphonium-based ionic liquids Kazama, Ryo; Matsumiya, Masahiko; Tsuda, Nanae Electrochimica Acta, Vol. 113 https://doi.org/10.1016/j.electacta.2013.09.082	journal	December 2013
Investigation of electrodeposition behavior for Nd(III) in [P2225][TFSA] ionic liquid by EQCM methods with elevated temperatures Ota, Hisashi; Matsumiya, Masahiko; Sasaya, Naoko Electrochimica Acta, Vol. 222 https://doi.org/10.1016/j.electacta.2016.11.038	journal	December 2016
The promoting effect of water on the electrodeposition of Eu in a dicyanamide ionic liquid Ehrenburg, Maria R.; Molodkina, Elena B.; Mishchenko, Artem Electrochimica Acta, Vol. 379 https://doi.org/10.1016/j.electacta.2021.138169	journal	May 2021
Pseudo-concentrated electrolytes for lithium metal batteries Wang, Huaping; Liu, Jiandong; He, Jian eScience, Vol. 2, Issue 5 https://doi.org/10.1016/j.esci.2022.06.005	journal	September 2022
Development of energy-saving recycling process for rare earth metals from voice coil motor by wet separation and electrodeposition using metallic-TFSA melts Ishioka, Kota; Matsumiya, Masahiko; Ishii, Mai Hydrometallurgy, Vol. 144-145 https://doi.org/10.1016/j.hydromet.2014.02.007	journal	April 2014
Vibrational spectra and structure of borohydrides D’Anna, Vincenza; Lawson Daku, Latévi Max; Hagemann, Hans Journal of Alloys and Compounds, Vol. 580 https://doi.org/10.1016/j.jallcom.2013.01.112	journal	December 2013
Electrodeposition of metals and alloys from ionic liquids Liu, Fan; Deng, Yida; Han, Xiaopeng Journal of Alloys and Compounds, Vol. 654 https://doi.org/10.1016/j.jallcom.2015.09.137	journal	January 2016
Recycling of rare earths: a critical review Binnemans, Koen; Jones, Peter Tom; Blanpain, Bart Journal of Cleaner Production, Vol. 51 https://doi.org/10.1016/j.jclepro.2012.12.037	journal	July 2013
Assessing the energy requirements and global warming potential of the production of rare earth elements Weng, Zhehan; Haque, Nawshad; Mudd, Gavin M. Journal of Cleaner Production, Vol. 139 https://doi.org/10.1016/j.jclepro.2016.08.132	journal	December 2016
Analysis of coordination states for Dy(II) and Dy(III) complexes in ionic liquids by Raman spectroscopy and DFT calculation Matsumiya, Masahiko; Kazama, Ryo; Tsunashima, Katsuhiko Journal of Molecular Liquids, Vol. 215 https://doi.org/10.1016/j.molliq.2015.12.049	journal	March 2016
Assessing the environmental footprint of the production of rare earth metals and alloys via molten salt electrolysis Vahidi, Ehsan; Zhao, Fu Resources, Conservation and Recycling, Vol. 139 https://doi.org/10.1016/j.resconrec.2018.08.010	journal	December 2018
FT-IR spectra of inorganic borohydrides D’Anna, Vincenza; Spyratou, Alexandra; Sharma, Manish Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 128 https://doi.org/10.1016/j.saa.2014.02.130	journal	July 2014
Extraction of rare earth ions by tri-n-butylphosphate/phosphonium ionic liquids and the feasibility of recovery by direct electrodeposition Matsumiya, Masahiko; Kikuchi, Yuya; Yamada, Takahiro Separation and Purification Technology, Vol. 130 https://doi.org/10.1016/j.seppur.2014.04.021	journal	June 2014
Molten salt electrolysis and room temperature ionic liquid electrochemical processes for refining rare earth metals: Environmental and economic performance comparison Pérez-Cardona, Jesús R.; Huang, Tai-Yuan; Zhao, Fu Sustainable Energy Technologies and Assessments, Vol. 54 https://doi.org/10.1016/j.seta.2022.102840	journal	December 2022
New Basis Set Exchange: An Open, Up-to-Date Resource for the Molecular Sciences Community Pritchard, Benjamin P.; Altarawy, Doaa; Didier, Brett Journal of Chemical Information and Modeling, Vol. 59, Issue 11 https://doi.org/10.1021/acs.jcim.9b00725	journal	October 2019
Water-Facilitated Electrodeposition of Neodymium in a Phosphonium-Based Ionic Liquid Sanchez-Cupido, Laura; Pringle, Jennifer M.; Siriwardana, Amal L. The Journal of Physical Chemistry Letters, Vol. 10, Issue 2 https://doi.org/10.1021/acs.jpclett.8b03203	journal	January 2019
Efficient Room Temperature Neodymium Electrodeposition in a Calcium-Based Electrolyte Engmann, Eugene T.; Yuan, Yating; Diaz, Luis A. ACS Applied Engineering Materials, Vol. 1, Issue 8 https://doi.org/10.1021/acsaenm.3c00342	journal	July 2023
Correlating Electrochemical Behavior and Speciation in Neodymium Ionic Liquid Electrolyte Mixtures in the Presence of Water Sanchez-Cupido, Laura; Pringle, Jennifer M.; Siriwardana, Amal I. ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 37 https://doi.org/10.1021/acssuschemeng.0c04288	journal	September 2020
Facile Room-Temperature Electrodeposition of Rare Earth Metals in a Fluorine-Free Task-Specific Electrolyte Yuan, Yating; Gaugler, James; Fan, Juntian ACS Sustainable Chemistry & Engineering, Vol. 11, Issue 34 https://doi.org/10.1021/acssuschemeng.3c01519	journal	August 2023
Exploring Coordination of Neodymium in Ionic Liquid: Insights to Guide Sustainable Recovery Dobhal, Garima S.; Pham, Le Nhan; Tawfik, Sherif Abdulkader ACS Sustainable Chemistry & Engineering, Vol. 11, Issue 39 https://doi.org/10.1021/acssuschemeng.3c04920	journal	September 2023
Lanthanides and Actinides in Ionic Liquids Binnemans, Koen Chemical Reviews, Vol. 107, Issue 6 https://doi.org/10.1021/cr050979c	journal	June 2007
Ionic Liquids at Electrified Interfaces Fedorov, Maxim V.; Kornyshev, Alexei A. Chemical Reviews, Vol. 114, Issue 5 https://doi.org/10.1021/cr400374x	journal	March 2014
Covalent transition metal, lanthanide, and actinide tetrahydroborate complexes Marks, Tobin J.; Kolb, John R. Chemical Reviews, Vol. 77, Issue 2 https://doi.org/10.1021/cr60306a004	journal	April 1977
Error-Balanced Segmented Contracted Basis Sets of Double-ζ to Quadruple-ζ Valence Quality for the Lanthanides Gulde, Rebekka; Pollak, Patrik; Weigend, Florian Journal of Chemical Theory and Computation, Vol. 8, Issue 11 https://doi.org/10.1021/ct300302u	journal	September 2012
Lanthanide(III) and Actinide(III) Complexes [M(BH ₄ ) ₂ (THF) ₅ ][BPh ₄ ] and [M(BH ₄ ) ₂ (18-crown-6)][BPh ₄ ] (M = Nd, Ce, U): Synthesis, Crystal Structure, and Density Functional Theory Investigation of the Covalent Contribution to Metal-Borohydride Bonding Arliguie, Thérèse; Belkhiri, Lotfi; Bouaoud, Salah-Eddine Inorganic Chemistry, Vol. 48, Issue 1 https://doi.org/10.1021/ic801685v	journal	January 2009
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
Raman Spectroscopic Studies and Ab Initio Calculations on Conformational Isomerism of 1-Butyl-3-methylimidazolium Bis-(trifluoromethanesulfonyl)amide Solvated to a Lithium Ion in Ionic Liquids: Effects of the Second Solvation Sphere of the Lithium Ion Umebayashi, Yasuhiro; Mori, Shuto; Fujii, Kenta The Journal of Physical Chemistry B, Vol. 114, Issue 19 https://doi.org/10.1021/jp100898h	journal	April 2010
Plating and stripping calcium in an organic electrolyte Wang, Da; Gao, Xiangwen; Chen, Yuhui Nature Materials, Vol. 17, Issue 1 https://doi.org/10.1038/nmat5036	journal	November 2017
Electrodeposition of neodymium and dysprosium from organic electrolytes Geysens, Pieter; Lin, Pin-Cheng; Fransaer, Jan Physical Chemistry Chemical Physics, Vol. 23, Issue 15 https://doi.org/10.1039/D0CP06606K	journal	January 2021
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Property-optimized Gaussian basis sets for lanthanides Rappoport, Dmitrij The Journal of Chemical Physics, Vol. 155, Issue 12 https://doi.org/10.1063/5.0065611	journal	September 2021
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals Mardirossian, Narbe; Head-Gordon, Martin Molecular Physics, Vol. 115, Issue 19 https://doi.org/10.1080/00268976.2017.1333644	journal	April 2017
Removal of Iron and Boron by Solvent Extraction with Ionic Liquids and Recovery of Neodymium Metal by Direct Electrodeposition Matsumiya, Masahiko; Yamada, Takahiro; Kikuchi, Yuya Solvent Extraction and Ion Exchange, Vol. 34, Issue 6 https://doi.org/10.1080/07366299.2016.1218692	journal	August 2016
Experimental and computational studies on solvent-free rare-earth metal borohydridesR(BH4)3(R=Y, Dy, and Gd) Sato, Toyoto; Miwa, Kazutoshi; Nakamori, Yuko Physical Review B, Vol. 77, Issue 10 https://doi.org/10.1103/PhysRevB.77.104114	journal	March 2008
Electrodeposition of rare earth metals Y, Gd, Yb in ionic liquids Glukhov, L. M.; Greish, A. A.; Kustov, L. M. Russian Journal of Physical Chemistry A, Vol. 84, Issue 1 https://doi.org/10.1134/S0036024410010206	journal	December 2009
Investigation of Oxidation State of the Electrodeposited Neodymium Metal Related with the Water Content of Phosphonium Ionic Liquids Kondo, Hitomi; Matsumiya, Masahiko; Tsunashima, Katsuhiko ECS Transactions, Vol. 50, Issue 11 https://doi.org/10.1149/05011.0529ecst	journal	March 2013
Development of Recycling Process for Rare Earth Magnets by Electrodeposition Using Ionic Liquids Media Ishii, Mai; Matsumiya, Masahiko; Kawakami, Satoshi ECS Transactions, Vol. 50, Issue 11 https://doi.org/10.1149/05011.0549ecst	journal	March 2013
Electrochemistry in Room Temperature Ionic Liquids: A Review and Some Possible Applications Silvester, Debbie S.; Compton, Richard G. Zeitschrift für Physikalische Chemie, Vol. 220, Issue 10, p. 1247-1274 https://doi.org/10.1524/zpch.2006.220.10.1247	journal	October 2006
Prospects for the Development of the Russian Rare-Earth Metal Industry in View of the Global Energy Transition—A Review Cherepovitsyn, Alexey; Solovyova, Victoria Energies, Vol. 15, Issue 1 https://doi.org/10.3390/en15010387	journal	January 2022
Metal Borohydrides beyond Groups I and II: A Review Suárez-Alcántara, Karina; Tena García, Juan Rogelio Materials, Vol. 14, Issue 10 https://doi.org/10.3390/ma14102561	journal	May 2021

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Title: Spectroscopic Insight on Neodymium Solvation in Lithium Borohydride-Supported Electrolyte

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