Perfluorinated Alkyl Chains Research Articles

A Computational and Spectroscopic Analysis of Solvate Ionic Liquids Containing Anions with Long and Short Perfluorinated Alkyl Chains.

Anion-driven, nanoscale polar-apolar structural organization is investigated in a solvate ionic liquid (SIL) setting by comparing sulfonate-based anions with long and short perfluorinated alkyl chains. Representative SILs are created from 1,2-bis(2-methoxyethoxy)ethane ("triglyme" or "G3"), lithium nonafluoro-1-butanesulfonate, and lithium trifluoromethanesulfonate. Molecular dynamics simulations, density functional theory computations, and vibrational spectroscopy provide insight into the overall liquid structure, cation-solvent interactions, and cation-anion association. Significant competition between G3 and anions for cation-binding sites characterizes the G3-LiC4F9SO3 mixtures. Only 50% of coordinating G3 molecules form tetradentate complexes with Li+ in [(G3)1Li][C4F9SO3]. Moreover, the SIL is characterized by extensive amounts of ion pairing. Based on these observations, [(G3)1Li][C4F9SO3] is classified as a "poor" SIL, similar to the analogous [(G3)1Li][CF3SO3] system. Even though the comparable basicity of the CF3SO3- and C4F9SO3- anions leads to similar SIL classifications, the hydrophobic fluorobutyl groups support extensive apolar domain formation. These apolar moieties permeate throughout [(G3)1Li][C4F9SO3] and persist even at relatively low dilution ratios of [(G3)10Li][C4F9SO3]. By way of comparison, the CF3 group is far too short to sustain polar-apolar segregation. This demonstrates how chemically modifying the anions to include hydrophobic groups can impart unique nanoscale organization to a SIL. Moreover, tuning these nano-segregated fluorinated domains could, in principle, control the presence of dimensionally ordered states in these mixtures without changing the coordination of the lithium ions.

Tailoring the Surface Enrichment of a Pt Catalyst in Ionic Liquid Solutions by Choice of the Solvent

AbstractThe so‐called buoy‐effect, that is, the targeted surface enrichment of a Pt catalyst dissolved in ionic liquids (ILs), is achieved by attaching perfluorinated alkyl chains to the ligand system, which drags the metal complex toward the interface. Using angle‐resolved X‐ray photoelectron spectroscopy, it is demonstrated how this surface enrichment can be tailored by variation of the solvent IL. In [CnC1Im][PF6] ILs (n = 2, 4, 8), the surface is fully saturated with the complex at 10%mol bulk content, while in [C4C1Im][Tf2N] only at 20%mol saturation is observed. At low catalyst concentrations of 1%mol, where saturation is not yet reached, the enrichment increases with decreasing length of the IL alkyl chain. As a general rule, the degree of surface enrichment decreases with the decrease in surface tension of the solvent IL, that is, in the order [C2C1Im][PF6] > [C4C1Im][PF6] > [C8C1Im][PF6] > [C4C1Im][Tf2N]. In ILs with very low surface tension, enrichment is even suppressed. These results reveal the surface tension of the solvent IL as rational parameter for tailoring the interfacial structure of IL‐based catalyst systems, such as supported ionic liquid phase (SILP) catalysis, where the nature of the IL/gas interface is expected to strongly influence the performance of the process.

Thermochemistry of Gas-Phase Thermal Oxidation of C2 to C8 Perfluorinated Sulfonic Acids with Extrapolation to C16.

New ideal-gas thermochemistry Cp°(T), H°(T), S°(T), and G°(T) are predicted for 53 species involved in the thermal destruction of perfluorinated sulfonic acids (PFSAs) ranging from C2 to C8 in perfluorinated alkyl chain length. Species were selected by considering both the pyrolytic and oxidative pathways of PFSA destruction. After the sulfur-containing moieties are removed, subsequent reactions largely involve species from a prior set of thermochemistry for the thermal destruction of perfluorinated carboxylic acids (Ram et al., J. Phys. Chem. A, 2024, 128, 7, 1313-1326). Enthalpies of formation at 0 K are computed using a new isogyric reaction scheme. Rigid-rotor harmonic-oscillator partition functions were calculated over a 200-2500 K temperature range using rovibrational properties at G4 (≤C3S1 species) and M06-2X-D3(0)/def2-QZVPP (≥C4S1 species), employing the 1D hindered rotor approximation to correct for torsional modes. Seven-coefficient NASA polynomial fits are reported in standardized formats. Bond dissociation energies and important reaction equilibria are examined to provide insights into the reactivity of potentially persistent species. Extrapolated NASA polynomials are also systematically predicted for 126 species larger than C8/C8S1 in size, allowing reasonably accurate estimates of thermochemistry without the need for expensive electronic structure calculations.

Grain boundary passivation by alkylammonium salt for highly stable perovskite solar cells

Perovskite solar cells (PSCs) are a strong candidate for next-generation photovoltaics, but their long-term stability poses challenges for use as a future renewable energy source. In particular, ambient moisture causes detrimental effects on not only the stability but also performance of PSCs. Herein, alkylammonium salts with perfluorinated long alkyl chains are introduced to passivate the grain boundaries and form hydrophobic surfaces. The perfluorinated alkyl chain moiety introduced into the perovskite layer reduces defect density and suppresses nonradiative recombination, thereby enhancing carrier transport capability and achieving a power conversion efficiency (PCE) of 20.31 %. Given the hydrophobic effects of fluorinated compounds on PSCs, about 90 % of the initial PCE can be retained after 1,000 h of continuous operation under a relative humidity of ∼ 40 % without encapsulation. The proposed additive strategy thus enables long-term operational stability of PSCs under humid conditions.

Ionic Liquid Functionalized Gel Polymer Electrolytes for Stable Lithium Metal Batteries

AbstractMetallic lithium (Li) is regarded as the ideal anode material in lithium‐ion batteries due to its low electrochemical potential, highest theoretical energy density and low density. There are, however, still significant challenges to be addressed such as Li‐dendrite growth and low interfacial stability, which impede the practical application of Li metal anodes. In order to circumvent these shortcomings, herein, we present a gel polymer electrolyte containing imidazolium ionic liquid end groups with a perfluorinated alkyl chain (F‐IL) to achieve both high ionic conductivity and Li ion transference number by fundamentally altering the solubility of salt within the gel electrolyte through Lewis‐acidic segments in the polymer backbone. Moreover, the presence of F‐IL moieties decreased the binding affinity of Li cation towards the glycol chains, enabling a rapid transfer of Li cation within the gel network. These structural features enabled the immobilization of anions on the ionic liquid segments to alleviate the space‐charge effect while promoting stronger anion coordination and weaker cation coordination in the Lewis‐acidic polymers. Accordingly, we realized a high Li ion conductivity (9.16×10−3 S cm−1) and high Li ion transference number of 0.69 simultaneously, along with a good electrochemical stability up to 4.55 V, while effectively suppressing Li dendrite growth. Moreover, the gel polymer electrolyte exhibited stable cycling performance of the Li|Li symmetric cell of 9 mAh cm−2 for more than 1800 hours and retained 86.7 % of the original capacity after 250 cycles for lithium‐sulfur (Li‐S) full cell.

Ionic Liquid Functionalized Gel Polymer Electrolytes for Stable Lithium Metal Batteries.

Metallic lithium (Li) is regarded as the ideal anode material in lithium‐ion batteries due to its low electrochemical potential, highest theoretical energy density and low density. There are, however, still significant challenges to be addressed such as Li‐dendrite growth and low interfacial stability, which impede the practical application of Li metal anodes. In order to circumvent these shortcomings, herein, we present a gel polymer electrolyte containing imidazolium ionic liquid end groups with a perfluorinated alkyl chain (F‐IL) to achieve both high ionic conductivity and Li ion transference number by fundamentally altering the solubility of salt within the gel electrolyte through Lewis‐acidic segments in the polymer backbone. Moreover, the presence of F‐IL moieties decreased the binding affinity of Li cation towards the glycol chains, enabling a rapid transfer of Li cation within the gel network. These structural features enabled the immobilization of anions on the ionic liquid segments to alleviate the space‐charge effect while promoting stronger anion coordination and weaker cation coordination in the Lewis‐acidic polymers. Accordingly, we realized a high Li ion conductivity (9.16×10−3 S cm−1) and high Li ion transference number of 0.69 simultaneously, along with a good electrochemical stability up to 4.55 V, while effectively suppressing Li dendrite growth. Moreover, the gel polymer electrolyte exhibited stable cycling performance of the Li|Li symmetric cell of 9 mAh cm−2 for more than 1800 hours and retained 86.7 % of the original capacity after 250 cycles for lithium‐sulfur (Li‐S) full cell.

Antioxidant Additive with a High Dielectric Constant for High Photo‐Oxidative Stabilization of Organic Solar Cells without Almost Sacrificing Initial High Efficiencies

Apart from power conversion efficiency (PCE) being the most important feature that requires improvement for organic solar cells (OSCs), their long‐term stability is another key factor for their successful commercialization. In fact, the lifetime of OSCs is severely limited by photoinduced oxidation, which occurs because of light radiation and the ingress of moisture (H2O) and oxygen (O2) within an ambient atmosphere. Herein, dibutylhydroxytoluene (BHT)‐based nonvolatile antioxidant additives with polar cyanide (CN) and perfluorinated alkyl chains (designated as BHT–CN and BHT–PF) are developed, demonstrating that the OSCs will have significantly improved long‐term stability by using them when exposed to the combined action of all the aforementioned stresses. In particular, the use of BHT–PF in the various given test‐bed OSC systems can remarkably enhance the long‐term stability, as well as the high initial PCEs similar to the maximized values obtained from the highly optimized OSCs with each well‐known suitable solvent additive. The promising results are attributed to the simultaneously enhanced dielectric and radical scavenging properties induced by the BHT–PF embedded in the active‐layer matrices. Taking its easy applicability into consideration, the BHT–PF is very useful in fabricating OSC modules that should be stable under severe photo‐oxidation conditions.

Attractive fluorine···fluorine interactions between perfluorinated alkyl chains: a case of perfluorinated Cu(II) diiminate Cu[C2F5–C(NH)–CF=C(NH)–CF3]2

Abstract A synthesis of the perfluorinated copper diiminate complex Cu[C2F5–C(NH)–CF=C(NH)–CF3]2 (3) and its self-assembly into infinite 1D chains in the crystal via Type II C(sp3)–F···F–C(sp3) contacts between perfluoroethyl substituents is reported. Rare Type II F···F interactions were studied by DFT calculations and topological analysis of the electron density distribution within the formalism of Bader’s theory (QTAIM method). This is the first report which discusses Type II contacts between perfuoroalkyl chains.

Helical nanofibers of N-(perfluorooctanoyl)cysteine ethyl ester in coordination polymers of Ag.

We propose using the formation of coordination polymers of Ag+ to probe differences between the perfluorinated alkyl chain and the alkyl chain by deriving a thiol ligand, N-(perfluoroalkanoyl)cysteine. Rapid formation in EtOH of P-/M-helical nanofibrils of high thermostability was found for N-(perfluorooctanoyl)-l-/d-cysteine ethyl esters at the μM level upon mixing with Ag+, but not for the octanoyl counterpart. This difference was also observed in terms of circular dichroism-enantiomeric excess dependence.

Fragmentation studies of neutral per- and polyfluoroalkyl substances by atmospheric pressure ionization-multiple-stage mass spectrometry.

The establishment of fragmentation pathways has a great interest in the identification of new or unknown related compounds present in complex samples. On that way, tentative fragmentation pathways for the ions generated by atmospheric pressure ionization of neutral per- and polyfluorinated alkyl substances (PFASs) have been proposed in this work. Electrospray (ESI), atmospheric pressure chemical ionization (APCI) and photoionization (APPI) were evaluated using mobile phases and source conditions that enhance the ionization efficiency of ions generated. A hybrid mass spectrometer consisting of a linear ion trap and an Orbitrap was used to combine the information of both multiple-stage mass spectrometry (MSn) and mass accuracy measurements to characterize and establish the genealogical relationship between the product ions observed. The ionization mechanisms to generate ions such as [M-H]-, [M]-•, and [M+O2]-• or the in-source collision-induced dissociation (CID) fragment ions in each API source are discussed in this study. In general, fluorotelomer olefins (FTOs) ionized in negative-ion APCI and APPI generated the molecular ion, while fluorotelomer alcohols (FTOHs) also provided the deprotonated molecule. Besides, fluorooctane sulfonamides (FOSAs) and sulfonamido-ethanols (FOSEs) led to the deprotonated molecule and in-source CID fragment ions, respectively. The fragmentation pathways from these precursor ions mainly involved initial α,β-eliminations of HF units and successive losses of CF2 units coming from the perfluorinated alkyl chain. Moreover, FTOHs and FOSEs showed a high tendency to generate adduct ions under negative-ion ESI and APPI conditions. The fragmentation study of these adduct ions has demonstrated a strong interaction with the attached moiety. Graphical abstract.

Comparison of LiTDI and LiPDI salts and influence of their perfluoroalkyl side-chain on association and electrochemical properties in triglyme

For the first time, the effect of minor structural changes to the electrolyte salt on solution properties is investigated experimentally. It was achieved by decomposition of the overall changes into individual components. It allowed to obtain information on the contradicting effects influence on the final result. This study is focused on comparison of two lithium salts: lithium 4,5-dicyano-2-(trifluoromethyl) imidazolide (LiTDI) and lithium 4,5-dicyano-2-(pentafluoroethyl) imidazolide (LiPDI). LiTDI is a very promising salt for lithium-ion battery application. PDI− anion differs from TDI− only in length of perfluorinated alkyl chain. Triethylene glycol dimethyl ether (triglyme) solutions of both salts in a wide range of concentrations were prepared. Triglyme was chosen as a solvent due to number of oxygen atoms which allows for fulfilment of lithium cation coordination sphere. Use of such similar salts in a model system allows us to find the correlation between salt structure and properties of electrolyte. Conductivity, viscosity, lithium transference number, thermal properties and FTIR spectra were measured for all solutions. Ionic fractions were also estimated by Fuoss-Kraus formalism. Obtained results showed that electrochemical properties of electrolyte are result of several opposing factors. Transference numbers are mostly dependent on association. We have also observed interesting correlation between thermal properties and conductivity.

Self-assembly of fluoride-encapsulated polyhedral oligomeric silsesquioxane (POSS) nanocrystals

The self-assembly and crystal packing of a unique series of nanocrystalline fluoride ion-encapsulated polyhedral oligomeric silsesquioxane (F-POSS) compounds, with substituted electron-withdrawing group (EWG) perfluorinated alkyl chain arms of varying lengths, were investigated.

Ionic Liquid-Containing Pickering Emulsions Stabilized by Graphene Oxide-Based Surfactants.

Emulsions stabilized by particles (i.e., Pickering emulsions) are complementary to those stabilized by small molecules or polymers and most commonly consist of oil droplets dispersed in a continuous water phase, with particles assembled at the fluid-fluid interface. New particle surfactants and different fluid-fluid interfaces are critical for developing next-generation systems for a number of advanced applications. Herein we report the preparation of IL-containing emulsions stabilized by graphene oxide (GO)-based nanoparticles using the IL [Bmim][PF6]: GO nanosheets stabilize IL-in-water emulsions, and alkylated GO nanosheets (C18-GO) stabilize IL-in-oil emulsions. The impact of particle concentration, fluid-fluid ratio, and addition of acid or base on emulsion formation and stability is studied, with distinct effects for the water and oil systems observed. We then illustrate the broad applicability of GO-based particle surfactants by preparing emulsions with different ILs and preparing inverted emulsions (water-in-IL and oil-in-IL emulsions). The latter systems were accessed by tuning the polarity of GO nanosheets by functionalization with a perfluorinated alkyl chain such that they were dispersible in IL. This work provides insight into the preparation of different IL-containing emulsions and lays a foundation for the architecture of dissimilar materials into composite systems.

Novel Perfluorinated Triblock Amphiphilic Copolymers for Lipid-Shelled Microbubble Stabilization.

Amphiphilic triblock (Atri) copolymers made of perfluorinated alkyl chain linked to hydrocarbon chain and methoxy-poly(ethylene glycol) of three different molecular weights were synthesized. In vitro evaluation demonstrated that these new compounds were noncytotoxic. Characterization and interaction of each triblock copolymer with a branched polyamine myristoyl lipid (2-{3[bis-(3-amino-propyl)-amino]-propylamino}- N-ditetradecyl carbamoyl methyl-acetamide, DMAPAP) were studied by the Langmuir film method and thermal analysis. The triblock copolymer/cationic lipids (1:10, w/w) were mixed with perfluorobutane gas to form microbubbles (MBs). The latter were characterized by optical microscopy to get the microbubble size and concentration by densimetry to determine the amount of encapsulated gas and by ultrasound to assess oscillation properties. Atri with the lowest and intermediate weights were shown to interact with the cationic lipid DMAPAP and stabilize the Langmuir film. In that case, monodisperse microbubbles ranging from 2.3 ± 0.1 to 2.8 ± 0.1 μm were obtained. The proportion of encapsulated gas within the MB shell increased up to 3 times after the incorporation of the copolymer with the lowest and intermediate weights. Moreover, the acoustic response of the microbubbles was maintained in the presence of the copolymers.

Study of TiO2 in anatase form on selected properties of new aliphatic-aromatic imines with bent shape towards organic electronics

ABSTRACTTwo bent-shaped imines (9E)-N-(3-((E)-(4-hexadecylphenylimino)methyl)benzylidene)-4-hexadecylbenzenamine (SL1) and (10E)-N-(3-((E)-(4-(perfluorooctyl)phenylimino)methyl)benzylidene)-4-(perfluorooctyl)benzenamine (SL2) were prepared by condensation reaction in N,N-dimethylacetamide to study their thermal, structural and electrochemical properties, as well as their mixtures with titanium dioxide. Chemical structure, temperature and TiO2 influences on the phase transition temperatures, enthalpy, texture and molecular dynamics of both imines were investigated by differential scanning calorimetry, polarising optical microscopy and Fourier transform middle-infrared absorption spectroscopy during heating and cooling. Changes in the surface morphology of the imines and their mixtures with TiO2 were registered by atomic force microscopy. X-ray study showed the tendency to form lamellas in the case of SL2 as an effect of the presence of two terminal perfluorinated alkyl chains connected to a polar mobile aromatic core, which resulted in microsegregation. Additionally, TiO2 influences the energy gap and HOMO–LUMO levels of imines as was detected by cyclic voltammetry. Finally, devices with two types of architectures, such as ITO/TiO2/SL1(or P3HT)/Au and ITO/TiO2/SL1:P3HT/Au were constructed and investigated under irradiation intensity of 97.7 mW/cm2.

Influence of the curing temperature on the diffusion rate of the perfluorinated alkyl chains of a modified epoxy resin

Perfluorononanoic acid (F17) was grafted to an epoxy resin. The virgin epoxy resin and the fluorinated epoxy resin were cured at various temperatures. Both air-resin and substrate-resin interfaces of the cured materials were characterized in terms of: (i) free surface energy, (ii) surface composition, evaluated using angle-resolved X-ray photoelectron spectroscopy (AR-XPS). Fluorine proportion was quantified at probing depths of about 4.5 and 9nm. The curing temperature highly influenced the diffusion of the perfluorinated chains towards both interfaces. Depending on the curing conditions, very low free surface energies (17mJ/m2) due to high fluorine concentrations (fluorine/carbon ratio=0.6) were measured at the air-resin interface. However, the F17 diffusion towards the substrate was also observed and led to important fluorine concentrations (F/C up to 0.4). Finally, a two-step curing procedure was used for monitoring the F17 diffusion during the curing, illustrated by an accumulation of fluorine atoms at both interfaces. A non-linear relation was highlighted between the surface energy drop and the fluorine content measured by AR-XPS.

Platinum Nanoparticles Modified with Perfluorinated Alkylamines as a Model Cathode Catalyst for Fuel Cells

AbstractPlatinum nanoparticles (NPs) modified with undecafluorohexylamine (UFHA) and octylamine were synthesized as a novel model cathode catalyst for fuel cells. The modified Pt NPs were well characterized by FTIR, X‐ray photoelectron spectroscopy, thermogravimetric analysis, and transmission electron microscopy. These NPs supported on carbon black were applied as electrocatalysts for the oxygen reduction reaction. The UFHA‐modified Pt NP catalyst showed high electrocatalytic activity and durability compared to a commercial catalyst. Besides suppression of undesired oxide formation on the Pt surface, the affinity between the perfluorinated alkyl chains of UFHA and Nafion® improved the catalyst activity by creating a desirable proton conduction path. Additionally, UFHA modification improved durability by suppressing Pt dissolution and carbon corrosion because of restricted water accessibility. The β‐oxide formation, which is responsible for Pt dissolution, was significantly attenuated by surface modification.

Synthesis and Characterization of New Fluorinated Tetrazines Displaying a High Fluorescence Yield.

Following the case of tetrazines substituted with perfluorinated alkyl chains, separated by two methylene groups from the tetrazine core, a new series of analogous tetrazines, but featuring only one methylene group between the fluorescent core and the perfluorinated chain, have been synthesized, and their photo-physical properties investigated. Their fluorescence quantum yields in acetonitrile are in same range than chloroalkoxytetrazines, which make them interesting candidates for light emission. Surprisingly, the quantum yields are lower with one methylene group, rather than two methylene groups separating the fluorinated chain from the emitting core, in the case of unsymmetrical compounds, while they are superior in the case of symmetrical ones. This unusual observation is discussed in the article.

A perfluorinated moiety-grafted carbon nanotube electrode for the non-aqueous lithium-oxygen battery.

A perfluorinated alkyl chain grafted to carbon nanotubes is employed in the lithium-oxygen (Li-O2) cell. We demonstrate a highly localized Li-O2 electrochemical reaction in close proximity to the perfluorinated moiety owing to its high O2 affinity. This hydrophobic modification can provide an enhancement in capacity for a very thin microbattery system.

Extended Tests of Pyrazolides As Lithium Salts for Lithium-Ion Cells

Lithium ion batteries nowadays dominate the market of high power energy storage devices [1]. One of the crucial points for next generation lithium batteries and dual-ion cells for stationary energy storage is the development of lithium salts with enhanced electrochemical stability and without corrosive impact at Al current collectors. Additionally, novel electrolytes for lithium batteries should have a high conductivity and should guarantee long term stability of anode and cathode interfaces as well as lead to stable SEI films. Here, we introduce first examples of a new generation of lithium salts based on pyrazolide anions [2] (cf. Fig. 1). The cyclic anion contains different perfluorinated side chains RF at the 3- and 5-position. Further tests were done with additional modifications at the anionic structure. Fig. 1: Structures and half-cell cycling with different discharge rates of the anionic pyrazolides and their modified types, RF representing perfluorinated alkyl chains of different lengths.Both, an efficient synthetic route as well as a thorough characterization of electrochemical stability and conductivity as well as cell tests were carried out. The salts showed an excellent electrochemical stability in non-aqueous solvents up to +5 V vs. Li/Li+. Moreover, cycling of LiFePO4 half-cells revealed structure-conductivity relationships for the novel salts. Both salt-types allowed at least 200 full cycles. Thus, the novel class lithium salts exhibits promising candidates for novel liquid and polymeric electrolyte systems and future safe lithium ion batteries.The authors acknowledge funding by the German federal ministry of education and research (BMBF) within the project “Insider”, No. 03EK3031A.[1] M. Winter, R. J. Brodd, Chemical Reviews, 104, 4245, 2004.[2] M. Grünebaum, H.-D. Wiemhöfer, M.M. Hiller, WO2013135824 A2, 2012.