Supramolecular Ionic‐Liquid Gels with High Ionic Conductivity

Maršavelski, Aleksandra; Smrečki, Vilko; Vianello, Robert; Žinić, Mladen; Moguš‐Milanković, Andrea; Šantić, Ana

doi:10.1002/chem.201500887

Cited by 25 publications

(27 citation statements)

References 43 publications

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“…GC-MS analyses were run with a Shimadzu QP50 using a Rtx-5MS column (30 m × 0.25 mm × 0.10 µm); injector temperature of 260 °C; He as carrier (1 mL min ) were added to a Fischer-Porter reactor containing the appropriate amount of catalyst (0.1 µmol Pd). After that, the reactor was pressurized with H 2 (2, 3, 4, 5, 6 or 8 bar) and heated (20,40,60,80 or 100 °C). Samples were taken from the reaction mixture and the conversion and selectivity were determined by GC analysis of the reaction samples.…”

Section: Mechanistic and Kinetic Studiesmentioning

confidence: 99%

Catalytically Active Membranelike Devices: Ionic Liquid Hybrid Organosilicas Decorated with Palladium Nanoparticles

et al. 2016

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Ionic liquid (IL)-hybrid organosilicas based on 1-n-butyl-3-(3-trimethoxysilylpropyl)-imidazolium cations associated with hydrophilic and hydrophobic anions decorated with well dispersed and similar sized (1.8-2.1 nm) Pd nanoparticles (PdNPs) are amongst the most active and selective catalysts for the partial hydrogenation of conjugated dienes to monoenes. The location of the sputter-imprinted Pd-NPs on different supports, as determined by RBS and HS-LEIS analysis, is modulated by the strength of the contact ion pair formed between the imidazolium cation and the anion, rather than the IL-hybrid organosilica pore size and surface area. In contrast, the pore diameter and surface area of the hybrid supports display a direct correlation with the anion hydrophobicity. XPS analysis showed that the Pd(0) surface component decreases with increasing ionic bond strength between the imidazolium cation and the anions (contact ion pair). The finding is corroborated by changes in the coordination number associated with the Pd-Pd scattering in EXAFS measurements. Hence, the interaction of the IL with the metal surface is found to occur via IL contact pairs (or aggregates). The observed selectivities of ≥99% to monoenes at full diene conversion indicate that the selectivity is intrinsic to the electron deficient Pd-metallic surfaces in this "restricted" ionic environment. This suggests that ILhybrid organosilica/Pd-NPs under multiphase conditions ("dynamic asymmetric mixture") operate akin to catalytically active membranes, i.e. far from the thermodynamic equilibrium. Detailed kinetic investigations show that the reaction rate is zero-order with respect to hydrogen and dependent on the fraction of catalyst surfaces covered by either the substrate and/or the product. The reaction proceeds via rapid inclusion and sorption of the diene to the IL/Pd metal surface saturated with H species. This is followed by reversible hydride migration to generate a π-allyl intermediate. The reductive elimination of this intermediate, the formal ratedetermining step (RDS), generates the alkene that is rapidly expelled from the IL phase to the organic phase.

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Section: Mechanistic and Kinetic Studiesmentioning

confidence: 99%

Catalytically Active Membranelike Devices: Ionic Liquid Hybrid Organosilicas Decorated with Palladium Nanoparticles

et al. 2016

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“…Previous reports demonstrated that the conductivity of ionogels is at best equal to or slightly higher than that of neat IL. Aleksandra and coworkers have also reported slightly higher ionic conductivity of supramolecular ionogel than that of neat ionic liquid 1-butyl 3-methyl imidazolium tetrafluoroborate [48]. High ionic conductivity of PEDOT: PSS/IL films as compared with that of pure PEDOT: PSS and IL have been published by Liu et al Origin of this higher value of conductivity was attributed to interactions between poly ionic PEDOT; PSS and IL.…”

Section:  (2)mentioning

confidence: 80%

Crosslinked thermoelectric hydro-ionogels: A new class of highly conductive thermoelectric materials

Sajid

Sabri

Said

et al. 2019

Energy Conversion and Management

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In this work, a new class of highly-conductive chemically cross-linked gel has been synthesized by the confinement of water and IL N, N, N triethyl octyl ammonium bromide ([N 2228 ] Br) in polyethylene glycol dimethacrylate (PEGDMA) matrix, using in situ thermally initiated radical polymerization loaded with 1 wt. % free radical initiator azobisisobutyronitrile (AIBN). This novel gel was named as hydroionogel (HIG). The thermoelectric properties of HIG such as ionic conductivity, Seebeck coefficient, and thermal conductivity were measured and owing to its high thermoelectric performance, we referred to this as crosslinked thermoelectric hydro-ionogel, henceforth will be denoted by X-TEHIG. For all the measurements, coin cells were fabricated using commercial LIR 2032 stainless steel battery casings with X-TEHIG sandwiched between the two graphene electrodes. The ionic conductivity of X-TEHIG was examined via AC impedance spectroscopy technique by using a Gamry apparatus. Remarkably, the ionic conductivity of X-TEHIG was higher than that of neat [N 2228 ] Br. A linear increase in ionic conductivity of X-TEHIG as a function of temperature was recorded that showed a considerably higher value of 74 mScm -1 at 70 °C. The origin of this high conductivity is attributed to interactions between PEGDMA monomers and cations and anions of the IL and formation of hydrogen bonds between water and Branion, O-H•••Br -. X-TEHIG demonstrated a higher Seebeck coefficient of 1.38 mVK -1 . The Fourier transform infrared (FTIR) spectroscopy results revealed the successful polymerization of X-TEHIG by the disappearance of C=C peak of methacrylate group in the spectrum of PEGDMA. These results suggest that X-TEHIG may be a potential candidate for thermoelectric applications owing to their high values of ionic conductivity and Seebeck coefficient.

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“…In this way all of the reported computational data correspond to the gas-phase Gibbs free energies at a temperature of 298.15 K and a pressure of 1 atm. The choice of such a computational setup was prompted by our recent success in modeling the properties of gelator molecules [23] and metal binding affinities [24], as well as correctly reproducing thermodynamic and kinetic parameters of organic [25,26] and enzymatic [27] reactions. In order to circumvent problems with the flexibility of the investigated systems, we tried many different conformations in each studied case and report here the results corresponding to the most stable structures.…”

Section: Computational Detailsmentioning

confidence: 99%

“…The ability of oxalamide derivatives (1-4) to form supramolecular gels by means of extended hydrogen bonded chains has given rise to a rich field of synthetically and externally tunable soft materials, which has been the subject of intense investigation in recent years [5][6][7][8][9]23]. Addition of hydrochloric acid, various metal salts, or ions to the gels significantly affects their gelation properties.…”

Section: Disruption Of Gelsmentioning

confidence: 99%

The Metal Effect on Self-Assembling of Oxalamide Gelators Explored by Mass Spectrometry and DFT Calculations

Dabić

Brkljačić²,

Tandarić

et al. 2017

J. Am. Soc. Mass Spectrom.

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Gels formed by self-assembly of small organic molecules are of wide interest as dynamic soft materials with numerous possible applications, especially in terms of nanotechnology for functional and responsive biomaterials, biosensors, and nanowires. Four bis-oxalamides were chosen to show if electrospray ionization mass spectrometry (ESI-MS) could be used as a prediction of a good gelator and also to shed light on the gelation processes. By inspecting the gelation of several solvent, we showed that bis(amino acid)oxalamide 1 proved to be the most efficient, also being able of forming the largest observable assemblies in the gas phase. The formation of singly charged assemblies holding from one up to six monomer units is the outcome of the strong intermolecular H-bonds, particularly among terminal carboxyl groups. The variation of solvents from polar aprotic towards polar protic did not have any significant effects on the size of the assemblies. The addition of a salt such as NaOAc or Mg(OAc), depending on the concentration, altered the assembling. Computational analysis at the DFT level aided in the interpretation of the observed trends and revealed that individual gelator molecules spontaneously assemble to higher aggregates, but the presence of the Na cation disrupts any gelator organization since it becomes significantly more favorable for gelator molecules to bind Na cations up to the 3:1 ratio than to self-assemble, being fully in line with experimental observations reported here. Graphical Abstract ᅟ.

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Supramolecular Ionic‐Liquid Gels with High Ionic Conductivity

Cited by 25 publications

References 43 publications

Catalytically Active Membranelike Devices: Ionic Liquid Hybrid Organosilicas Decorated with Palladium Nanoparticles

Catalytically Active Membranelike Devices: Ionic Liquid Hybrid Organosilicas Decorated with Palladium Nanoparticles

Crosslinked thermoelectric hydro-ionogels: A new class of highly conductive thermoelectric materials

The Metal Effect on Self-Assembling of Oxalamide Gelators Explored by Mass Spectrometry and DFT Calculations

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