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1. Confinement Effects in Dynamics of Ionic Liquids with Polymer‐Grafted Nanoparticles

   https://doi.org/10.1002/cphc.202200219  

   Liu, Siqi ; Li, Ruhao ; Tyagi, Madhusudan ; Akcora, Pinar ( June 2022 , ChemPhysChem)

   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.
2. Dynamics of ionic liquids in the presence of polymer-grafted nanoparticles

   https://doi.org/10.1039/c9nr04204k  

   Liu, Siqi ; Liedel, Clemens ; Tarakina, Nadezda V. ; Osti, Naresh C. ; Akcora, Pinar ( October 2019 , Nanoscale)

   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.
3. Non-solvating, side-chain polymer electrolytes as lithium single-ion conductors: synthesis and ion transport characterization

   https://doi.org/10.1039/c9py01035a  

   Liu, Jiacheng ; Pickett, Phillip D. ; Park, Bumjun ; Upadhyay, Sunil P. ; Orski, Sara V. ; Schaefer, Jennifer L. ( January 2020 , Polymer Chemistry)

   Solid-state single-ion conducting polymer electrolytes have drawn considerable interest for secondary lithium batteries due to their potential for high electrochemical stability and safety, but applications are limited by their low ionic conductivities. Specifically, poly(ethylene oxide) (PEO) based electrolytes have the highest reported Li + conductivities for these materials; however, their potential is limited due to the ion transport mechanism being coupled to segmental relaxations of the cation solvating polymer chain. To investigate the potential of single-ion conducting polymer electrolytes lacking polar matrices, we synthesized three para -polyphenylene-based, side-chain polymer electrolytes with various pendent anion chemistries (–SO 3 − , –PSI − , and –TFSI − ) with differing binding affinities to Li + . Compared with the previously reported lithium poly(4-styrenesulfonyl(trifluoromethylsulfonyl)imide) (LiPSTFSI), the side-chain polymers showed at least 3 orders of magnitude higher conductivity with the same –TFSI − anion (6.7 × 10 −6 S cm −1 compared with 1.2 × 10 −10 S cm −1 at 150 °C). We found that the side-chain electrolyte showed a dielectric relaxation dominated transport mechanism through use of dielectric spectroscopy analysis. The conductivity is highly dependent on the charge delocalization and size of the pendent anion, which provides a pathway forward for themore »engineering of polymeric ion conductors for electrochemical applications.« less
4. Understanding the Mechanism of Star-Block Copolymers as Nanoreactors for Synthesis of Well-Defined Silver Nanoparticles

   Zhu, Albert ; Li, Qiong ; Chen, Xiaoyi ( August 2018 , Journal of emerging investigators)

   Facile and large-scale synthesis of well-defined, thermally stable silver nanoparticles protected by polymer brushes for use in practical applications is still a challenge. Recent work has reported a nanoreactor approach that can be used to synthesize these silver nanoparticles. This approach uses amphiphilic star-block copolymers, which have a hydrophilic core surrounded by a hydrophobic exterior. These polymers thus can serve as the nanoreactors. In this study, we hypothesize that the local high concentration of silver ions in the inner hydrophilic cores of these star-block copolymers facilitates the nucleation and subsequent growth of silver nanoparticles. When all silver nanoparticles nucleate from the cores of the star-block copolymers in solution, the particle size can be controlled by the core size of the polymer. To test this hypothesis, a polyisoprene-b-poly(p-tert-butylstyrene) (PI-b-PtBS) star-block copolymer was functionalized with carboxylic acid groups using a high-efficiency, photo-initiated thiol-ene click reaction. We characterized this modified polymer using proton nuclear magnetic resonance spectroscopy, and the results indicated that ~60% of the double bonds in the polyisoprene block were successfully functionalized with carboxylic acid groups. When silver ions were added to a solution of these functionalized star-block copolymers, the negatively charged carboxylic acid groups would attract the positively charged silvermore »ions. Subsequent reduction of these Ag+ by a tert-butylamine-borane complex at room temperature produced nanosized silver particles. However, transmission electron microscopy images showed that a significant amount of relatively large silver nanoparticles grew outside the star-block copolymer nanoreactors.« less
5. Effect of Changing Interfacial Tension on Fragmentation Kinetics of Block Copolymer Micelles

   https://doi.org/10.1021/acs.macromol.2c02158  

   Gupta, Supriya ; Lodge, Timothy P. ( February 2023 , Macromolecules)

   Micelle fragmentation, one of the key mechanisms responsible for equilibration of kinetically trapped micelles, is investigated for block copolymer micelles in ionic liquids. In particular, the role of driving force for micelle fragmentation is studied by altering the solvent quality after micelle preparation, amounting to a jump in interfacial tension γ between solvent and the micelle core. Direct dissolution of a 1,2-polybutadiene-b-poly(ethylene oxide) copolymer (Mn = 17.5 kDa and fPEO = 0.38) in the ionic liquid [C2mim][TFSI] results in large micelles with average size 〖"〈" "R" _"h" "〉" 〗_"∘" " ≈ 68" nm and dispersity "Đ ≈ 1.27" . The solution of the as-prepared micelles is then diluted by the careful addition of a second ionic liquid [C10mim][TFSI] having lower γ with the micelle core, such that the micelles remain unaffected. The γ and hence the quality of the solvent mixture was controlled by the degree of dilution. The choice of the second solvent is based on the measurement of γ for a series of [Cxmim][TFSI] ILs with 1-2-polybutadiene homopolymer, carried out using a pendant drop test. Diluting the micelles by adding another ionic liquid with lower γ tends to decrease the equilibrium micelle size which, in turn, enhances themore »driving force for fragmentation of the bigger as-prepared micelles, represented by increase in the ratio of aggregation numbers Q/Qeq. Subjecting the diluted micellar solution to temperature-jump to 170 °C followed by thermal annealing leads to fragmentation of the as-prepared micelles to attain a near-equilibrium state. The micelles are characterized using in-situ dynamic light scattering technique to observe the time evolution of average micelle size, from which the relaxation time is obtained. Additionally, small-angle X-ray scattering and cryogenic transmission electron microscopy measurements were carried out to obtain the micelle core size and distribution in the micellar solutions before and after fragmentation. The enhancement in the driving force achieved by controlling the amount of low γ solvent resulted in faster fragmentation; the characteristic fragmentation time decreases monotonically on increasing the size ratio Q/Qeq from 1.2 to 5.« less