Anion Architecture Controls Structure and Electroresponsivity of Anhalogenous Ionic Liquids in a Sustainable Fluid Article Swipe

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S. Li , Oliver S. Hammond , Andrew Nelson , Liliana de Campo , Michael Moir , Carl Recsei , Manishkumar R. Shimpi , Sergei Glavatskih , Georgia A. Pilkington , Anja‐Verena Mudring , Mark W. Rutland ·

YOU? · · 2024 · Open Access · · DOI: https://doi.org/10.1021/acs.jpcb.3c08189

Three nonhalogenated ionic liquids (ILs) dissolved in 2-ethylhexyl laurate (2-EHL), a biodegradable oil, are investigated in terms of their bulk and electro-interfacial nanoscale structures using small-angle neutron scattering (SANS) and neutron reflectivity (NR). The ILs share the same trihexyl(tetradecyl)phosphonium ([P_6,6,6,14]⁺) cation paired with different anions, bis(mandelato)borate ([BMB]^-), bis(oxalato)borate ([BOB]^-), and bis(salicylato)borate ([BScB]^-). SANS shows a high aspect ratio tubular self-assembly structure characterized by an IL core of alternating cations and anions with a 2-EHL-rich shell or corona in the bulk, the geometry of which depends upon the anion structure and concentration. NR also reveals a solvent-rich interfacial corona layer. Their electro-responsive behavior, pertaining to the structuring and composition of the interfacial layers, is also influenced by the anion identity. [P_6,6,6,14][BOB] exhibits distinct electroresponsiveness to applied potentials, suggesting an ion exchange behavior from cation-dominated to anion-rich. Conversely, [P_6,6,6,14][BMB] and [P_6,6,6,14][BScB] demonstrate minimal electroresponses across all studied potentials, related to their different dissociative and diffusive behavior. A mixed system is dominated by the least soluble IL but exhibits an increase in disorder. This work reveals the subtlety of anion architecture in tuning bulk and electro-interfacial properties, offering valuable molecular insights for deploying nonhalogenated ILs as additives in biodegradable lubricants and supercapacitors.

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Ionic liquid Ion Architecture Ionic bonding Chemistry Chemical engineering Materials science Organic chemistry Engineering Art Catalysis Visual arts

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Type: article
Language: en
Landing Page: https://doi.org/10.1021/acs.jpcb.3c08189
PDF: https://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.3c08189
OA Status: hybrid
Cited By: 3
References: 72
Related Works: 10
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DOI: https://doi.org/10.1021/acs.jpcb.3c08189

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Title: Anion Architecture Controls Structure and Electroresponsivity of Anhalogenous Ionic Liquids in a Sustainable Fluid

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Language: en

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Publication year: 2024

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Publication date: 2024-04-19

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Authors: S. Li, Oliver S. Hammond, Andrew Nelson, Liliana de Campo, Michael Moir, Carl Recsei, Manishkumar R. Shimpi, Sergei Glavatskih, Georgia A. Pilkington, Anja‐Verena Mudring, Mark W. Rutland

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Landing page: https://doi.org/10.1021/acs.jpcb.3c08189

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Concepts: Ionic liquid, Ion, Architecture, Ionic bonding, Chemistry, Chemical engineering, Materials science, Organic chemistry, Engineering, Art, Catalysis, Visual arts

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Cited by: 3

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