skip to main content


Title: Dynamics of ionic liquids in the presence of polymer-grafted nanoparticles
We incorporated polymer-grafted nanoparticles into ionic and zwitterionic liquids to explore the solvation and confinement effects on their heterogeneous dynamics using quasi-elastic neutron scattering (QENS). 1-Hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) mixed with deuterated poly(methyl methacrylate) (d-PMMA)-grafted nanoparticles is studied to unravel how dynamic coupling between PMMA and HMIM-TFSI influence the fast and slow diffusion characteristics of the HMIM + cations. The zwitterionic liquid, 1-butyl-3-methyl imidazole-2-ylidene borane (BMIM-BH 3 ) is critically selected and mixed with PMMA-grafted nanoparticles for comparison in this work as its ions do not self-dissociate and it does not couple with PMMA through ion-dipole interactions as HMIM-TFSI does. We find that long-range unrestricted diffusion of HMIM + cations is higher in well-dispersed particles than in aggregated particle systems, whereas the localized diffusion of HMIM + is measured to be higher in close-packed particles. Translational diffusion dynamics of BMIM-BH 3 is not influenced by any particle structures suggesting that zwitterions do not interact with PMMA. This difference between two ionic liquid types enables us to decouple polymer effects from the diffusion of ionic liquids, which is integral to understand the ionic transport mechanism in ionic liquids confined in polymer-grafted nanoparticle electrolytes.  more » « less
Award ID(s):
1807802
NSF-PAR ID:
10232788
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Nanoscale
Volume:
11
Issue:
42
ISSN:
2040-3364
Page Range / eLocation ID:
19832 to 19841
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Ionic liquid mixed with poly(methyl methacrylate)-grafted nanoparticle aggregates at low particle concentrations was shown to exhibit different dynamics and ionic conductivity than that of pure ionic liquid in our previous studies. In this work, we report on the quasi-elastic neutron scattering results on ionic liquid containing polymer-grafted nanoparticles at the higher particle concentration. The diffusivity of imidazolium (HMIM + ) cations of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) in the presence of poly(methyl methacrylate)-grafted iron oxide nanoparticles and the ionic conductivity of solutions were discussed through the confinement. Analysis of the elastic incoherent structure factor suggested the confinement radius decreased with the addition of grafted particles in HMIM-TFSI/solvent mixture, indicating the confinement that is induced by the high concentration of grafted particles, shrinks the HMIM-TFSI restricted volume. We further conjecture that this enhanced diffusivity occurs as a result of the local ordering of cations within aggregates of poly(methyl methacrylate)-grafted particles. 
    more » « less
  2. The use of ionic liquids as solvent for polymers or polymer-grafted nanoparticles provides an exciting feature to explore electrolyte-polymer interaction. 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIm-TFSI) holds specific interactions with the polymer through ion-dipole or hydrogen bonding. For this work, poly(methyl methacrylate)-b-poly(styrene sulfonate) (PMMA-b-PSS) copolymer-grafted Fe3O4 nanoparticles with different sulfonation levels (~4.9-10.9 mol% SS) were synthesized and their concentration dependent ionic conductivities were reported in acetonitrile and HMIm-TFSI/acetonitrile mixture. We found that conductivity enhancement with the particle concentration in acetonitrile was due to the aggregation of grafted particles, hence sulfonic domain connectivity. The ionic conductivity was found to be related to the effective hopping transfer within ionic channels. To the contrary, the conductivity decreased or remained constant with increasing particle concentration in HMIm-TFSI/acetonitrile. This result was attributed to the ion coupling between ionic liquid and copolymer domains. 
    more » « less
  3. Abstract

    Ionic liquids (ILs) are promising electrolytes for high‐performance Li‐ion batteries (LIBs), which can significantly improve the safety and energy storage capacity. Although extensive experimental and computational studies have reported, further exploration is needed to understand the properties of IL systems, their microscopic structures and dynamics, and the behavior of Li ions in ILs. We report here results of molecular dynamics simulations as a function of electric field for Li diffusion in two IL systems, [EMIM][TFSI] and [BMIM][TFSI] doped with various concentrations of LiTFSI. We find that the migration of each individual Li ion depends largely on its micro‐environment, leading to differences by factors of up to 100 in the diffusivity. The structural and dynamical properties indicate that Li diffusion is affected significantly by the coordination and interaction with the oxygen species in the TFSI anions. Moreover, the IL cations also contribute to the Li diffusion mechanism by attenuating the Li–TFSI interaction.

     
    more » « less
  4. Abstract

    Multiphase suspensions are complex systems where microscopic interactions between suspended bubbles, particles, and liquids can significantly alter bulk behavior. Observing the internal mechanics of such suspensions can help constrain the dynamics of natural multiphase flows. To capture these internal processes at high speed and in three dimensions, we propose the use of Swept Confocally Aligned Planar Excitation (SCAPE) microscopy in analog experiments. This imaging technique, developed for neuroscience and biology, uses a sweeping light sheet to illuminate and image fluorophores within a sample. We performed experiments using water and various oils as the liquid phases, glass or PMMA particles for solids, and air or CO2for gas, which we imaged at rates >50 volumes per second, over a volume size of ∼1 × 1 × 0.4 mm. We focused on three case studies: (1) bubble nucleation, growth, and rise in sparkling water, where we found that bubble detachment from angular PMMA particles left residual bubbles that also grew and detached, generating more bubbles compared to smooth particles; (2) flow of immiscible liquids (water droplets suspended in canola oil) in a porous matrix of PMMA beads, which highlighted the importance of pore and throat sizes on droplet velocities; and (3) injection of air bubbles into concentrated suspensions of glass beads or crushed PMMA particles in a refractive‐index‐matched liquid, which revealed particle motion and strong alterations of the bubble shape. We conclude that SCAPE microscopy is a powerful tool to study the dynamics of multiphase systems.

     
    more » « less
  5. Abstract BACKGROUND

    Knoevenagel condensation is an important tool for building carbon–carbon (CC) bonds, especially when catalyzed by enzymes to enable a potentially high chemo‐, regio‐ and/or stereoselectivity. Although many Knoevenagel condensation reactions are carried out in aqueous solutions, insoluble hydrophobic substrates often lead to poor catalytic efficiencies. The use of water‐miscible organic solvents improves the substrate solubilization, but usually induces activity suppression or inactivation of enzymes. There is a great need to develop alternative solvents for both substrate dissolution and enzyme compatibility in CC bond formation reactions.

    RESULTS

    Our group previously developed dual‐functionalized water‐mimicking ionic liquids (ILs) for the activation and stabilization of hydrolases (e.g. lipase and protease). In the present study, we evaluated the Knoevenagel condensation of 4‐chlorobenzaldehyde with acetylacetone, and found that porcine pancreas lipase in water‐mimicking ILs carrying ammonium, imidazolium and benzimidazolium cations enabled higher reaction rates (up to 3.22 μmol min−1 g−1lipase) and better yields thantert‐butanol, glymes and [BMIM][Tf2N]. Interestingly, tertiary amide solvents such asN‐methyl‐2‐pyrrolidone (NMP),N,N‐dimethylformamide (DMF) andN,N‐dimethylacetamide (DMAc) led to 8.2‐ to 11.1‐fold increases in the initial rate (up to 35.66 μmol min−1 g−1lipase) when compared with dual‐functionalized ILs, which is likely due to some synergistic effect of these tertiary amides with the lipase.

    CONCLUSION

    Dual‐functionalized ILs based on ammonium, imidazolium and benzimidazolium cations improved Knoevenagel condensation reaction rates and yields when compared withtert‐butanol and glymes. Tertiary amides (NMP, DMF and DMAc) significantly increased the reaction rate. © 2024 The Authors.Journal of Chemical Technology and Biotechnologypublished by John Wiley & Sons Ltd on behalf of Society of Chemical Industry (SCI).

     
    more » « less