| 1. |
- Mushtaq, Irrum, et al.
(författare)
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Ferrocene-Based Terpolyamides and Their PDMS-Containing Block Copolymers: Synthesis and Physical Properties
- 2022
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Ingår i: Polymers. - : MDPI. - 2073-4360. ; 14:23
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Tidskriftsartikel (refereegranskat)abstract
- Aromatic polyamides are well-known as high-performance materials due to their outstanding properties making them useful in a wide range of applications. However, their limited solubility in common organic solvents restricts their processability and becomes a hurdle in their applicability. This study is focused on the synthesis of processable ferrocene-based terpolyamides and their polydimethylsiloxane (PDMS)-containing block copolymers, using low-temperature solution polycondensation methodology. All the synthesized materials were structurally characterized using FTIR and 1H NMR spectroscopic techniques. The ferrocene-based terpolymers and block copolymers were soluble in common organic solvents, while the organic analogs were found only soluble in sulfuric acid. WXRD analysis showed the amorphous nature of the materials, while the SEM analysis exposed the modified surface of the ferrocene-based block copolymers. The structure–property relationship of the materials was further elucidated by their water absorption and thermal behavior. These materials showed low to no water absorption along with their high limiting oxygen index (LOI) values depicting their good flame-retardant behavior. DFT studies also supported the role of various monomers in the polycondensation reaction where the electron pair donation from HOMO of diamine monomer to the LUMO of acyl chloride was predicted, along with the calculation of various other parameters of the representative terpolymers and block copolymers.
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| 2. |
- Ahmed, Mukhtiar, et al.
(författare)
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Aromatic Heterocyclic Anion Based Ionic Liquids and Electrolytes
- 2023
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 25:4, s. 3502-3512
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Tidskriftsartikel (refereegranskat)abstract
- Five new ionic materials comprising fluorine-free aromatic heterocyclic anions based on pyridine and pyrazine combined with a common n-tetrabutylphosphonium cation, (P4444)+, result in two room temperature ionic liquids (RTILs), one semi-solid, and two organic ionic plastic crystals (OIPCs) with melting points >20 °C. The OIPCs showed a plastic crystalline phase, multiple solid–solid transitions, and plastic crystalline and melt phases. For both the neat RTILs and the Li+ conducting electrolytes, the nature and strength of the ion–ion interactions mainly depend on the position of the nitrogen atom with respect to the carboxylate group in the anions. Furthermore, for the RTILs the ionic conductivity is effected by the electronic structure and flexibility of the ions and the anions diffuse faster than the (P4444)+ cation, but are slowed down in the electrolytes due to the strong electrostatic interactions between the carboxylate group of the anions and the Li+, as shown both experimentally and computationally. Overall, this study describes the effect of structural tuning of aromatic anions on the ion–ion interactions and introduces new ionic materials with promising properties to be used as solid and liquid electrolytes in energy storage devices.
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| 3. |
- Ahmed, Mukhtiar
(författare)
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Fluorine-Free Ionic Liquids and Electrolytes : From Synthesis to Energy Storage Applications
- 2023
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Since their introduction by Sony in 1990, lithium-ion batteries (LIBs) have acquired a sizable market share. They have the best energy densities, a high open circuit voltage, a low self-discharge rate, no memory effect, and a slow loss of charge when not in use. These properties make them the most popular rechargeable batteries for portable gadgets, electric vehicles and aerospace applications. They do, however, pose major safety issues since the conventional electrolytes are made of fluorinated salts dissolved in volatile organic solvents, the former being meta-stable at ambient temperature and the latter being flammable with a high vapour pressure. Thus, there is an urge to develop thermally and electrochemically stable non-fluorinated electrolytes to improve the safety and performance of batteries. Electrolytes based on ionic liquids (ILs) offer a range of advantages over traditional electrolytes including low volatility and high thermal and electrochemical stabilities, and can additionally be made fluorine-free and task-specific. In addition, the transport properties of ILs can be controlled by structural design of chemical functionalities to reduce the ionic interactions and enhance the ion mobilities.This thesis is focussed on the development of new fluorine-free ILs and electrolytes for safer energy storage applications. An overview of synthesis, physicochemical and electrochemical characterizations of six different families of ILs and their structurally analogous electrolytes based on the aromatic heterocyclic rings, oligoether based aromatic and aliphatic carboxylates, oligoether phosphates and aromatic sulfonyl anions coupled with n- tetrabutylphosphonium-, imidazolium-, pyrrolidinium-based and alkali metal cations is presented. The structures and purity of the new anions, their intermediate products and the ILs are characterized by using multinuclear NMR, FTIR and mass spectrometry. These studies are further complemented by using NMR diffusometry to investigate the relative anion and anion mobilities and understand the possible interaction mechanisms between the oppositely charged ions within the ILs and the electrolytes, and especially, the influence of Li+ addition in the IL-based electrolytes. Among the synthesized ILs, the sulfonyl-based ILs revealed highest thermal stabilities, aromatic oligoether-based ILs showed the best electrochemical stabilities and aromatic sulfonyl -based ILs exhibited highest ionic conductivities. Some of the synthesized salts displayed promising performance as electrolytes in energy storage devices.
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| 4. |
- Ahmed, Mukhtiar, et al.
(författare)
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Ionic Liquids and Electrolytes with Flexible Aromatic Anions
- 2023
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Ingår i: Chemistry - A European Journal. - : John Wiley & Sons. - 0947-6539 .- 1521-3765. ; 29:41
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Tidskriftsartikel (refereegranskat)abstract
- Five new n-tetrabutylphosphonium (P4444)+ cation based ionic liquids (ILs) with oligoether substituted aromatic carboxylate anions have been synthesized. The nature and position of the oligoether chain affect thermal stability (up to 330 ºC), phase behaviour (Tg < -55 ºC) and ion transport. Furthermore, with the aim of application in lithium batteries, electrolytes were created for two of the ILs by 10 mol% doping using the corresponding Li-salts. This affects the ion diffusion negatively, from being higher and equal for cations and anions to lower for all ions and unequal. This is due to the stronger ionic interactions and formation of aggregates, primarily between the Li+ ions and the carboxylate group of the anions. Electrochemically, the electrolytes have electrochemical stability windows up to 3.5 V, giving some promise for battery application.
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| 5. |
- Ahmed, Mukhtiar, et al.
(författare)
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Pyrrolidium- and Imidazolium-Based Ionic Liquids and Electrolytes with Flexible Oligoether Anions
- 2024
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Ingår i: ChemPhysChem. - : John Wiley & Sons. - 1439-7641 .- 1439-4235. ; 25:9
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Tidskriftsartikel (refereegranskat)abstract
- A new class of fluorine-free ionic liquids (ILs) and electrolytes based on aliphatic flexible oligoether anions, 2-(2-methoxyethoxy)acetate (MEA) and 2-[2-(2-methoxyethoxy)ethoxy]acetate (MEEA), coupled with pyrrolidinium and imidazolium cations is introduced. For the ILs with MEEA anions, Li+ conducting electrolytes are created by doping the ILs with 30 mol % of LiMEEA. The structural flexibility of the oligoether functionality in the anion results in glass transition temperatures (Tg) as low as −60 °C for the neat ILs and the electrolytes. The imidazolium-based ILs and electrolytes reveal better thermal stabilities but higher Tg and lower electrochemical stabilities than the corresponding pyrrolidinium-based analogues. All neat ILs show comparable transport properties for the cations and these decrease by the addition of lithium salt – the pyrrolidinium-based electrolyte being affected the most.
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| 6. |
- An, Rong, et al.
(författare)
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Atomic force microscopy probing interactions and microstructures of ionic liquids at solid surfaces
- 2022
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Ingår i: Nanoscale. - : Royal Society of Chemistry. - 2040-3364 .- 2040-3372. ; 14:31, s. 11098-11128
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Forskningsöversikt (refereegranskat)abstract
- Ionic liquids (ILs) are room temperature molten salts that possess preeminent physicochemical properties and have shown great potential in many applications. However, the use of ILs in surface-dependent processes, e.g. energy storage, is hindered by the lack of a systematic understanding of the IL interfacial microstructure. ILs on the solid surface display rich ordering, arising from coulombic, van der Waals, solvophobic interactions, etc., all giving near-surface ILs distinct microstructures. Therefore, it is highly important to clarify the interactions of ILs with solid surfaces at the nanoscale to understand the microstructure and mechanism, providing quantitative structure–property relationships. Atomic force microscopy (AFM) opens a surface-sensitive way to probe the interaction force of ILs with solid surfaces in the layers from sub-nanometers to micrometers. Herein, this review showcases the recent progress of AFM in probing interactions and microstructures of ILs at solid interfaces, and the influence of IL characteristics, surface properties and external stimuli is thereafter discussed. Finally, a summary and perspectives are established, in which, the necessities of the quantification of IL–solid interactions at the molecular level, the development of in situ techniques closely coupled with AFM for probing IL–solid interfaces, and the combination of experiments and simulations are argued.
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| 7. |
- An, Rong, et al.
(författare)
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Controlling the nanoscale friction by layered ionic liquid films
- 2020
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 22:26, s. 14941-14952
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Tidskriftsartikel (refereegranskat)abstract
- The nanofriction coefficient of ionic liquids (ILs), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), on the surfaces of mica and graphite was investigated using atomic force microscopy (AFM). A pronounced layered spatial distribution was found in the IL film formed on the solid substrates and can be divided into 3 well distinguishable regions exhibiting different physical properties with increasing distance from the substrate. We found that the friction coefficient (μ) increases monotonically as the layering thickness decreases, no matter what the thickness of the bulk IL is. This suggests that the layering assembled IL at solid surfaces is more important than the bulk phase in determining the magnitude of the nanoscale friction. The increase in the friction coefficient as the layering thickness decreases is most likely attributed to the assembled ordered IL layers closer to the substrate surfaces having a greater activation barrier for unlocking the surfaces to allow shear.
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| 8. |
- An, Rong, et al.
(författare)
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Friction of Ionic Liquid–Glycol Ether Mixtures at Titanium Interfaces : Negative Load Dependence
- 2018
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Ingår i: Advanced Materials Interfaces. - : John Wiley & Sons. - 2196-7350. ; 5:14
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Tidskriftsartikel (refereegranskat)abstract
- Structural reorientation of alkyl chains in the phosphonium cation of orthoborate ionic liquid mixed with glycol ether occurs with increasing normal load of the AFM tip. The flat reoriented structure, similar to the ‘blooming lotus leaf’, produces a new sliding interface that is responsible for the observed lower friction at higher loads. This work is reported by Rong An, Liangliang Huang, Faiz Ullah Shah and co‐workers in article number 1800263.
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| 9. |
- An, Rong, et al.
(författare)
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Friction of Ionic Liquid–Glycol Ether Mixtures at Titanium Interfaces : Negative Load Dependence
- 2018
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Ingår i: Advanced Materials Interfaces. - : John Wiley & Sons. - 2196-7350. ; 5:14
-
Tidskriftsartikel (refereegranskat)abstract
- The atomic force microscopy experiments and nonequilibrium molecular dynamics (NEMD) simulations demonstrate a negative friction–load dependence to ionic liquid–glycol ether mixtures, that is, the friction decreases as the normal load increases. NEMD simulations reveal a structural reorientation of the studied ionic liquid (IL): as the normal load increases, the cation alkyl chains of ILs change the orientation to preferentially parallel to the tip scanning path. The flat‐oriented IL structures, similar to the “blooming lotus leaf,” produce a new sliding interface and reduce the friction. A further molecular dynamics simulation is carried out by adopting slit‐pore models to mimic the tip approaching process to confirm the dynamics of ILs. A faster diffusion of ILs in the smaller slit pore is observed. The faster diffusion of ILs in the more confined slit pore facilitates the structural reorientation of ILs. The resulted new sliding surface is responsible for the observed smaller friction at higher loads, also known as the negative friction–load dependence. These findings provide a fundamental explanation to the role of ILs in interfacial lubrications. They help to understand liquid flow properties under confinement, with implications for the development of better nanofluidic devices.
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| 10. |
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| 11. |
- An, Rong, et al.
(författare)
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Ionic liquids on uncharged and charged surfaces: In situ microstructures and nanofriction
- 2022
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Ingår i: Friction. - : Springer. - 2223-7690 .- 2223-7704. ; 10:11, s. 1893-1912
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Tidskriftsartikel (refereegranskat)abstract
- In situ changes in the nanofriction and microstructures of ionic liquids (ILs) on uncharged and charged surfaces have been investigated using colloid probe atomic force microscopy (AFM) and molecular dynamic (MD) simulations. Two representative ILs, [BMIM][BF4] (BB) and [BMIM][PF6] (BP), containing a common cation, were selected for this study. The torsional resonance frequency was captured simultaneously when the nanoscale friction force was measured at a specified normal load; and it was regarded as a measure of the contact stiffness, reflecting in situ changes in the IL microstructures. A higher nanoscale friction force was observed on uncharged mica and highly oriented pyrolytic graphite (HOPG) surfaces when the normal load increased; additionally, a higher torsional resonance frequency was detected, revealing a higher contact stiffness and a more ordered IL layer. The nanofriction of ILs increased at charged HOPG surfaces as the bias voltage varied from 0 to 8 V or from 0 to —8 V. The simultaneously recorded torsional resonance frequency in the ILs increased with the positive or negative bias voltage, implying a stiffer IL layer and possibly more ordered ILs under these conditions. MD simulation reveals that the [BMIM]+ imidazolium ring lies parallel to the uncharged surfaces preferentially, resulting in a compact and ordered IL layer. This parallel “sleeping” structure is more pronounced with the surface charging of either sign, indicating more ordered ILs, thereby substantiating the AFM-detected stiffer IL layering on the charged surfaces. Our in situ observations of the changes in nanofriction and microstructures near the uncharged and charged surfaces may facilitate the development of IL-based applications, such as lubrication and electrochemical energy storage devices, including supercapacitors and batteries.
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| 12. |
- An, Rong, et al.
(författare)
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On the Ionic Liquid Film ‘Pinned’ by Core-Shell Structured Fe3O4@Carbon Nanoparticles and Their Tribological Properties
- 2019
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 21:48, s. 26387-26398
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Tidskriftsartikel (refereegranskat)abstract
- A strongly ‘pinned’ ionic liquid (IL, [BMIM][PF6]) film onto silicon (Si) surface via carbon capsuled Fe3O4 core-shell (Fe3O4@C) nanoparticles is achieved, revealing excellent friction-reducing ability at a high load. The adhesion force is measured as ~ 198 nN at the Fe3O4@C-Si interface by Fe3O4@C colloidal AFM tip, which is stronger than that at both Fe3O4@C-Fe3O4@C (~ 60 nN) and IL-Si (~ 10 nN) interfaces, indicating a strong ‘normal pin-force’ towards the Si substrate. The resulting strengthened force enables the formation of lateral IL networks via the dipole-dipole attractions among Fe3O4 cores. The observed blue shift of the characteristic band related to the IL anion in ATR-FTIR spectra confirmed the enhanced interaction. The N-Si, P-O chemical bonds formed as a result of the IL interactions with the Si substrate confirmed by XPS spectroscopy suggested that the IL lay on the Si plane. This orientation is favorable for Fe3O4@C nanoparticles to exert ‘normal pin-force’ and press the IL film strongly onto surfaces. The IL ios/clusters are thus anchored by these Fe3O4@C ‘pins’ onto the substrate to form a dense film, resulting in a smaller interaction size parameter, which is responsible for the reduced friction coefficient μ.
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| 13. |
- Bhattacharyya, Shubhankar, et al.
(författare)
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Insights into the Effect of CO2 Absorption on the Ionic Mobility of Ionic Liquids
- 2016
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - 1463-9076 .- 1463-9084. ; 18:41, s. 28617-28625
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Tidskriftsartikel (refereegranskat)abstract
- We investigate a comparative effect of CO2 absorption on the ionic mobility of two choline based ionic liquids comprising two different anions such as threonine and imidazole. The synthesized ionic liquids were characterized using 1H and 13C NMR and other spectroscopic techniques. By keeping a common cation and changing the anion from threonine to imidazole both the viscosity and density reduced drastically. We found that [N1,1,6,2OH][Imi] exhibits the highest CO2 capture capacity at 20 °C of 5.27 mol of CO2 per kg of ionic liquid (1.27 mol of CO2 per mol of ionic liquid, 23.26 wt% of CO2) whereas [N1,1,6,2OH][Threo] exhibits 3.6 mol of CO2 per kg of ionic liquid (1.05 mol of CO2 per mol of ionic liquid, 15.87 wt% of CO2). The activation energy for diffusion is calculated using the Vogel-Fulcher-Tamman (VFT) equation in the form of diffusivity. It was found that the activation energy for the diffusion of [N1,1,6,2OH][Threo] is ∼10 times higher than that of [N1,1,6,2OH][Imi]. 1H diffusion NMR data revealed that the diffusivity of [N1,1,6,2OH][Imi] is increased after CO2 absorption whereas a decrease in diffusivity was observed in the case of [N1,1,6,2OH][Threo]. This anomalous behavior of [N1,1,6,2OH][Imi] was further explained by using DFT calculations.
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| 14. |
- Bhattacharyya, Shubhankar, et al.
(författare)
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Thermal stability of choline based amino acid ionic liquids
- 2018
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Ingår i: Journal of Molecular Liquids. - : Elsevier. - 0167-7322 .- 1873-3166. ; 266, s. 597-602
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Tidskriftsartikel (refereegranskat)abstract
- Thermal stability of different choline based amino acid ionic liquids were studied. Both short term as well as long term thermal studies were carried out. Long term thermal studies of all ILs were carried out by isothermal TGA and short term thermal studies were measured by temperature ramped TGA. Isothermal TGA were studied at two different temperatures 100 °C and 150 °C for 500 min. Whereas, short term thermal stability represents as T2%, T5% and T10% which are the temperature at which 2%, 5% and 10% mass loss of ILs were observed. The effect of alkyl side chain on the cation, etherification of the cation as well structural variation of anion on the thermal stability of choline based ILs were investigated. It was observed that thermal characteristics of ILs towards temperature ramped TGA were different compared to isothermal TGA.
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| 15. |
- Bhowmick, Sourav, et al.
(författare)
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Ambient temperature liquid salt electrolytes
- 2023
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Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1364-548X .- 1359-7345. ; 59:18, s. 2620-2623
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Tidskriftsartikel (refereegranskat)abstract
- Alkali metal salts usually have high melting points due to strong electrostatic interactions and solvents are needed to create ambient temperature liquid electrolytes. Here, we report on six phosphate-anion-based alkali metal salts, Li/Na/K, all of which are liquids at room temperature, with glass transition temperatures ranging from −61 to −29 °C, and are thermally stable up to at least 225 °C. While the focus herein is on various physico-chemical properties, these salts also exhibit high anodic stabilities, up to 6 V vs. M/M+ (M = Li/Na/K), and deliver some battery performance - at elevated temperatures as there are severe viscosity limitations at room-temperature. While the battery performance arguably is sub-par, solvent-free electrolytes based on alkali metal salts such as these should pave the way for conceptually different Li/Na/K-batteries, either by refined anion design or by using several salts to create eutectic mixtures.
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| 16. |
- Bhowmick, Sourav, et al.
(författare)
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Physical and electrochemical properties of new structurally flexible imidazolium phosphate ionic liquids
- 2022
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 24:38, s. 23289-23300
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Tidskriftsartikel (refereegranskat)abstract
- New structurally flexible 1-methyl- and 1,2-dimethyl-imidazolium phosphate ionic liquids (ILs) bearing oligoethers have been synthesized and thoroughly characterized. These novel ILs revealed high thermal stabilities, low glass transitions, high conductivity and wide electrochemical stability windows up to 6 V. Both anions and cations of 1-methyl-imidazolium ILs diffuse faster than the ions of 1,2-dimethyl-imidazolium ILs, as determined by pulsed field gradient nuclear magnetic resonance (PFG-NMR). The 1-methyl-imidazolium phosphate ILs showed relatively higher ionic conductivities and ion diffusivity as compare with the 1,2-dimethyl-imidazolium phosphate ILs. As expected, the diffusivity of all the anions and cations increases with an increase in the temperature. The 1-methyl-imidazolium phosphate ILs formed hydrogen bonding with the phosphate anions, the strength of which is decreased with increasing temperature, as confirmed by variable temperature 1H and 31P NMR spectroscopy. One of the representative IL, [EmDMIm][DEEP], presented a promising performance at elevated temperatures as an electrolyte in a supercapacitor composed of multiwall carbon nanotubes and activated charcoal (MWCNTs/AC) composite electrodes.
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| 17. |
- Bhowmick, Sourav, et al.
(författare)
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Structurally Flexible Pyrrolidinium- and Morpholinium-based Ionic Liquid Electrolytes
- 2023
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 25:29, s. 19815-19823
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Tidskriftsartikel (refereegranskat)abstract
- Ion transport measures and details as well as physico-chemical and electrochemical properties are presented for a small set of structurally flexible pyrrolidinium (Pyrr) and morpholinium (Morph) cation-based ionic liquids (ILs), all with oligoether phosphate-based anions. All have high thermal stabilities, low glass transition temperatures, and wide electrochemical stability windows, but rather moderate ionic conductivities, whereas both the anions and the cations of the Pyrr-based ILs diffuse faster than those of the Morph-based ILs. Overall the former ILs have significantly more promise as high-temperature supercapacitor electrolytes, rendering a specific capacitance of 164 F g−1 at 1 mV s−1, a power density of 241 W kg−1 and a specific energy density of 30 Wh kg−1 at 90 °C in a symmetric graphite supercapacitor.
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| 18. |
- Dong, Yihui, et al.
(författare)
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Phosphonium-Based Ionic Liquid Significantly Enhances SERS of Cytochrome c on TiO2 Nanotube Arrays
- 2022
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 14:23, s. 27456-27465
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Tidskriftsartikel (refereegranskat)abstract
- Surface-enhanced Raman scattering (SERS) is an attractive technique for studying trace detection. It is of utmost importance to further improve the performance and understand the underlying mechanisms. An ionic liquid (IL), the anion of which is derived from biomass, [P6,6,6,14][FuA] was synthesized and used as a trace additive to improve the SERS performance of cytochrome c (Cyt c) on TiO2 nanotube arrays (TNAs). An increased and better enhancement factor (EF) by four to five times as compared to the system without an IL was obtained, which is better than that from using the choline-based amino acid IL previously reported by us. Dissociation of the ILs improved the ionic conductivity of the system, and the long hydrophobic tails of the [P6,6,6,14]+ cation contributed to a strong electrostatic interaction between Cyt c and the TNA surface, thereby enhancing the SERS performance. Atomic force microscopy did verify strong electrostatic interactions between the Cyt c molecules and TNAs after the addition of the IL. This work demonstrates the importance of introducing the phosphonium-based IL to enhance the SERS performance, which will stimulate further development of more effective ILs on SERS detection and other relevant applications in biology.
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| 19. |
- Fan, Pengpeng, et al.
(författare)
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The effect of nanoscale friction of mesoporous carbon supported ionic liquids on the mass transfer of CO2 adsorption
- 2020
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 22:3, s. 1097-1106
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Tidskriftsartikel (refereegranskat)abstract
- Supported ionic liquids (ILs) are attractive alternatives for CO2 capture and the thickness of supported IL films plays a critical role in the CO2 mass transfer rate. However, the dependence of CO2 uptake on the IL film thickness differs as the system varies. In this work, atomic force microscopy (AFM) is employed to probe the ‘nanofriction coefficient’ to characterize the mobility of ILs at the solid interface, in which, the smaller the nanofriction coefficient, the faster are the ionic mobility and CO2 mass transfer. A monotonic and almost linear relationship for supported IL films is obtained between the resistance of CO2 mass transfer (1/k) and the nanofriction coefficient (μ), avoiding the controversy over the effect of supported IL film thickness on CO2 adsorption. The enhanced mass transfer of CO2 adsorption at IL-solid interfaces is observed at smaller resistance 1/k and friction coefficient μ. The low-friction driven local mobility (diffusion) of ILs at solid interfaces is enhanced, promoting the exchange mixing of the ILs adsorbing CO2 with the ‘blank-clean’ ions of the ILs, and thus accelerating the CO2 mass transfer. The proposed correlation links the nanoscale friction with the mass transfer of CO2 adsorption, providing a fresh view on the design of ultra-low frictional supported ILs for enhanced CO2 capture and separation processes.
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| 20. |
- Filippov, Andrei, PhD, 1957-, et al.
(författare)
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CO2 absorption and ion mobility in aqueous choline-based ionic liquids
- 2019
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Ingår i: Journal of Molecular Liquids. - : Elsevier. - 0167-7322 .- 1873-3166. ; 276, s. 748-752
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Tidskriftsartikel (refereegranskat)abstract
- CO2 absorption and ion mobility are investigated in a series of 50/50 wt% aqueous solutions of choline-based ionic liquids with different cations and anions: [N1,1,4,2OH][Threo], [N1,1,5,2OH][Threo], [N1,1,6,2OH][Threo], [N1,1,5,2OH][β-ala] and [N1,1,5,2OH][Tau]. The process of CO2 absorption was completed in an hour reaching maximum of absorption capacity 0.07–0.10 wt% to ionic liquid (by 0.4–0.6 molar ratios). A rapid CO2 absorption is observed by the formation of solid product as a result of reaction between CO2 molecule and the ionic liquid. Diffusion coefficients of the cation and anion in the mixture are comparable while the diffusivity of water molecules is found to be quite different from the ions. In the process of CO2 absorption, an increase in the diffusivity of ions is observed due to the precipitation of solid products and depletion of ions contents in the liquid phase of the system. 13C NMR measurements of diffusivity of CO2 enriched with 13C isotope showed that a part of the absorbed CO2 remained in the liquid phase being physically and chemically bound to ions. The ionic liquid is re-cycled by evaporating water and releasing CO2 molecules using vacuum and temperature.
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| 21. |
- Filippov, Andrei, PhD, 1957-, et al.
(författare)
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Diffusion of Ions in Phosphonium Orthoborate Ionic Liquids Studied by 1H and 11B Pulsed Field Gradient NMR
- 2020
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Ingår i: Frontiers in Chemistry. - : Frontiers Media S.A.. - 2296-2646. ; 8
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Tidskriftsartikel (refereegranskat)abstract
- Non-halogenated boron-based ionic liquids (ILs) composed of phosphonium cations and chelated orthoborate anions have high hydrolytic stability, low melting point and exceptional properties for various applications. This study is focused on ILs with the same type of cation, trihexyltetradecylphosphonium ([P6,6,6,14]+), and two orthoborate anions, such as bis(salicylato)borate ([BScB]−) and bis(oxalato)borate ([BOB]−). We compare the results of this study with our previous studies on ILs with bis(mandelato)borate ([BMB]−) and a variety of different cations (tetraalkylphosphonium, dialkylpyrrolidinium and dialkylimidazolium). The ion dynamics and phase behavior of these ILs is studied using 1H and 11B pulsed-field-gradient (PFG) NMR. PFG NMR is demonstrated to be a useful tool to elucidate the dynamics of ions in this class of phosphonium orthoborate ILs. In particular, the applicability of 11B PFG NMR for studying anions without 1H, such as [BOB]−, and the limitations of this technique to measure self-diffusion of ions in ILs are demonstrated and discussed in detail for the first time.
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| 22. |
- Filippov, Andrei, PhD, 1957-, et al.
(författare)
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Rapid carbene formation increasing ion diffusivity in an imidazolium acetate ionic liquid confined between polar glass plates
- 2019
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 21:40, s. 22531-22538
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Tidskriftsartikel (refereegranskat)abstract
- 1-Ethyl-3-methyl-imidazolium acetate ([EMIM][OAc]) is one of the most widely used ionic liquids for various applications. This study is focussed on the chemical stability of [EMIM][OAc] on the surfaces of polar glass plates. 1H and 13C NMR spectroscopy and NMR diffusometry of [EMIM][OAc] IL confined between glass plates with a specific surface area 105–106 m−1 are thoroughly investigated. A rapid and spontaneous reaction took place on the surfaces of glass plates leading to the formation of neutral chemical moieties as evident by the appearance of new signals in the 1H NMR spectra. These new products are assigned as N-heterocyclic carbene (NHC) and acetic acid. These neutral chemical moieties have significantly increased the ion diffusivity by dissociation of the cation and the anion in [EMIM][OAc] IL. The yield and rate of formation of NHC and acetic acid are found to increase with the increasing surface area of polar glass plates and the time of contact between the IL and glass surfaces. Based on NMR spectroscopy, a dissociative reaction mechanism is proposed for the formation of free NHC in the neat [EMIM][OAc] IL.
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| 23. |
- Filippov, Andrei, PhD, 1957-, et al.
(författare)
-
Reactivity of CO2 with aqueous choline-based ionic liquids probed by solid-state NMR spectroscopy
- 2019
-
Ingår i: Journal of Molecular Liquids. - : Elsevier. - 0167-7322 .- 1873-3166. ; 286
-
Tidskriftsartikel (refereegranskat)abstract
- CO2 absorption in a series of choline-based ionic liquids is investigated using solid-state 13C and 15N MAS NMR spectroscopy. Natural abundance and 13C enriched CO2 gas was purged through 50 wt% aqueous solutions of alkyldimethyl(2-hydroxyethyl)ammonium threonine, [N1,1,n,2OH][Threo], (alkyl = butyl, pentyl and hexyl) and pentyldimethyl(2-hydroxyethyl)ammonium taurine [N1,1,5,2OH][Tau]. The process of CO2 absorption results in precipitation of a solid sediment, which stays in equilibrium with the liquid phase. Upon degassing of the sample, the sediment is dissolved back into the IL-aqueous phase. Solid state 13C and 15N MAS NMR data suggest that the solid sediment is composed of neutral threonine (or taurine) in the zwitterionic forms and the liquid phase contained the products of reactions between the ionic liquids and CO2 molecules. A plausible mechanism for formation of the solid sediments and the reaction products in liquid phases is suggested.
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| 24. |
- Filippov, Andrei, PhD, 1957-, et al.
(författare)
-
Understanding the Interaction of Boric Acid and CO2 with Ionic Liquids in Aqueous Medium by Multinuclear NMR Spectroscopy
- 2020
-
Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 8:1, s. 552-560
-
Tidskriftsartikel (refereegranskat)abstract
- Boric acid is known to enhance the kinetics of CO2 absorption by some active aqueous solutions. However, the mechanism of interaction of boric acid with CO2 in the presence of active molecules is not yet fully understood. In this work, the interaction and dynamics of ions in aqueous solutions of functionalized choline-based ionic liquids [N1,1,5,2OH][Threo] and [N1,1,5,2OH][Tau] in the presence of boric acid and CO2 was thoroughly investigated using a multinuclear NMR approach: 13C and 11B NMR spectroscopy, 11B NMR transverse relaxation, and 1H and 11B NMR diffusometry. 13C and 11B NMR spectroscopy revealed the formation of borate-based complexes as a result of a reaction between boric acid and the anions of the ILs at ionic liquid/boric acid molar ratios larger than ca. 0.15. The formation of these complexes and their dynamics were further investigated using 11B relaxation and 1H and 11B pulse-field-gradient (PFG) NMR. Plausible reaction mechanisms of boric acid with the anions of the ILs, formation of the borate complexes, and dissociation of these complexes facilitated by CO2 molecules are suggested.
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| 25. |
- Filippov, Andrei, PhD, 1957-, et al.
(författare)
-
Unusual ion transport behaviour of ethylammonium nitrate mixed with lithium nitrate
- 2021
-
Ingår i: Journal of Molecular Liquids. - : Elsevier. - 0167-7322 .- 1873-3166. ; 340
-
Tidskriftsartikel (refereegranskat)abstract
- The diffusivity of ions and ionic conductivity of ethylammonium nitrate (EAN) mixed with lithium nitrate (LiNO3) has been carried out as a function of Li-salt concentration and temperature. An unusual behavior of ion diffusivities and ionic conductivities of the mixtures are observed over a range of Li-salt concentration and temperature. The diffusivities of EA+ and Li+, as measured by pulsed-field gradient (PFG) nuclear magnetic resonance (NMR) diffusometry, are found to be comparable in the lower temperature range. An overall decrease in the ion diffusivity is observed with an increase in the concentration of LiNO3. A lower degree of dissociation of ionic complexes in the presence lower concentration of the Li-salt (less than 6 mol. %) resulted in lower ionic conductivity. In the higher concentration range of Li-salt the Li+ diffusivity is monotonously decreased with an increase in the concentration. In the lower concentration range, the Li+ diffusivity exceeded the diffusivity of EA+ cation demonstrating the release of Li+ from the associates. Being enclosed between glass plates, the diffusivities of EA+ and Li+ showed peculiarities similar to the earlier observed results for neat nitrate ILs: accelerated diffusivity of cations and reversible alteration of diffusivities under the influence of strong static magnetic field.
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| 26. |
- Gnezdilov, Oleg I., et al.
(författare)
-
Translational and reorientational dynamics of ionic liquid-based fluorine-free lithium-ion battery electrolytes
- 2022
-
Ingår i: Journal of Molecular Liquids. - : Elsevier. - 0167-7322 .- 1873-3166. ; 345
-
Tidskriftsartikel (refereegranskat)abstract
- The translational as well as reorientational mobilities of fluorine-free electrolytes prepared by mixing lithium furan-2-carboxylate Li(FuA) salt with tetra(n-butyl)phosphonium furan-2-carboxylate (P4444)(FuA) ionic liquid are thoroughly investigated. The diffusivity of ions and T1 relaxation of protons belonging to various chemical groups of (P4444)+ and (FuA)− ions and the Li+ ion present in these electrolytes are measured as a function of lithium salt concentration and temperature. The temperature dependence of correlation time for reorientational mobility of various chemical groups of (P4444)+ and (FuA)− ions and the Li+ ion are estimated and used in calculations temperature dependence of the corresponding reorientational rates. It is shown that an increase in the concentration of lithium salt leads to a decrease in both the diffusion coefficients and the reorientation rates for all the chemical groups in concerted way. Activation energy of the reorientational rates for different chemical groups of the organic ions and the Li+ are discussed in details.
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| 27. |
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| 28. |
- Hafeez, Abdul, et al.
(författare)
-
Synthesis, Crystal Structures, and Spectroscopic Characterization of Bis-aldehyde Monomers and Their Electrically Conductive Pristine Polyazomethines
- 2019
-
Ingår i: Polymers. - : MDPI. - 2073-4360. ; 11:9
-
Tidskriftsartikel (refereegranskat)abstract
- Bis-aldehyde monomers 4-(4′-formyl-phenoxy)benzaldehyde (3a), 3-methoxy-4-(4′-formyl-phenoxy)benzaldehyde (3b), and 3-ethoxy-4-(4′-formyl-phenoxy)benzaldehyde (3c) were synthesized by etherification of 4-fluorobenzaldehyde (1) with 4-hydroxybenzaldehyde (2a), 3-methoxy-4-hydroxybenzaldehyde (2b), and 3-ethoxy-4-hydroxybenzaldehyde (2c), respectively. Each monomer was polymerized with p-phenylenediamine and 4,4′-diaminodiphenyl ether to yield six poly(azomethine)s. Single crystal X-ray diffraction structures of 3b and 3c were determined. The structural characterization of the monomers and poly(azomethine)s was performed by FT-IR and NMR spectroscopic techniques and elemental analysis. Physicochemical properties of polymers were investigated by powder X-ray diffraction, thermogravimetric analysis (TGA), viscometry, UV–vis, spectroscopy and photoluminescence. These polymers were subjected to electrical conductivity measurements by the four-probe method, and their conductivities were found to be in the range 4.0 × 10−5 to 6.4 × 10−5 Scm−1, which was significantly higher than the values reported so far.
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| 29. |
- Kanwal, Sehrish, et al.
(författare)
-
Poly-thiourea formaldehyde based anticorrosion marine coatings on type 304 stainless steel
- 2020
-
Ingår i: Journal of Materials Research and Technology. - : Elsevier. - 2238-7854 .- 2214-0697. ; 9:2, s. 2146-2153
-
Tidskriftsartikel (refereegranskat)abstract
- In the present study, hexamethylene diisocyanate (HMDI) encapsulated poly-thiourea formaldehyde (PTF) (10 wt%) coating was developed in an epoxy-polyamine matrix and their anticorrosion studies on Type SS304 stainless steel substrate have been conducted using electrochemistry techniques. The compact and hydrophobic shell wall of PTF proved to be a potent shell wall material for HMDI encapsulation. The effect of temperature and pH values was found to be decisive factor in the synthesis of microcapsules. The PTF microcapsules were synthesized in acidic condition with a pH value of 3. Over 90% of the core fraction is retained in water after 21 days immersion. However, core content decreased with increasing temperature. The capsules were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy(SEM), thermogravimetric analysis (TGA) and Electrochemical Impedance spectroscopy (EIS). Scanning electron microscopic analysis depicts the uniform morphology of coating with a particle size in the range of 1.08 μm–22.06 μm. The vibrational band at 2271 cm−1 attributed to NCO signal further endorses the successful encapsulation of HMDI into the PTF capsules. Electrochemical testing on steel specifies the appreciable anticorrosion performance of the synthesized poly thiourea formaldehyde (PTF) coating against artificial sea water.
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| 30. |
- Khan, Inayat Ali, et al.
(författare)
-
Effect of Aromaticity in Anion on the Cation–Anion Interactions and Ionic Mobility in Fluorine-Free Ionic Liquids
- 2020
-
Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 124:52, s. 11962-11973
-
Tidskriftsartikel (refereegranskat)abstract
- Ionic liquids (ILs) composed of tetra(n-butyl)phosphonium [P4444]+ and tetra(n-butyl)ammonium [N4444]+ cations paired with 2-furoate [FuA]−, tetrahydo-2-furoate [HFuA]−, and thiophene-2-carboxylate [TpA]− anions are prepared to investigate the effects of electron delocalization in anion and the mutual interactions between cations and anions on their physical and electrochemical properties. The [P4444]+ cations-based ILs are found to be liquids, while the [N4444]+ cations-based ILs are semi-solids at room temperature. Thermogravimetric analysis revealed higher decomposition temperatures and differential scanning calorimetry analysis showed lower glass transition temperatures for phosphonium-based ILs than the ammonium-based counterparts. The ILs are arranged in the decreasing order of their ionic conductivities as [P4444][HFuA] (0.069 mS cm–1) > [P4444][FuA] (0.032 mS cm–1) > [P4444][TpA] (0.028 mS cm–1) at 20 °C. The oxidative limit of the ILs followed the sequence of [FuA]−> [TpA]−> [HFuA]−, as measured by linear sweep voltammetry. This order can be attributed to the electrons’ delocalization in [FuA]− and in [TpA]− aromatic anions, which has enhanced the oxidative limit potentials and the overall electrochemical stabilities.
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| 31. |
- Khan, Inayat Ali, et al.
(författare)
-
Effect of structural variation in biomass-derived nonfluorinated ionic liquids electrolytes on the performance of supercapacitors
- 2022
-
Ingår i: Journal of Energy Chemistry. - : Elsevier. - 2095-4956 .- 2096-885X. ; 69, s. 174-184
-
Tidskriftsartikel (refereegranskat)abstract
- There is a growing interest in sustainable and high performance supercapacitors (SCs) operating at elevated temperatures as they are highly demanded in heat-durable electronics. Here, we present a biomass-derived nonfluorinated ionic liquid (IL) [P4444][HFuA] and its structural analogue [P4444][TpA] as electrolytes for supercapacitors comprising multiwall carbon nanotubes and activated charcoal (MWCNTs/AC) mixed carbon composite electrodes. A detailed investigation of the effect of scan rate, temperature, potential window and orientation of ions on the electrodes surfaces is performed. The supercapacitors exhibited relatively lower specific capacitance for both [P4444][HFuA] and [P4444][TpA] ILs at room temperature. However, the specific capacitance has significantly increased with an increase in temperature and potential window. The equivalent serie resistances of the SCs is deceased with increasing temperatures, which is a result of improved ionic conductivities of the IL electrolytes. In CV cycling at 60 °C, the capacitor with [P4444][HFuA] IL-based electrolyte retained about 90% of its initial capacitance, while the capacitor with [P4444][TpA] IL-based electrolyte retained about 83% of its initial capacitance. Atomistic computations revealed that the aromatic [FuA]− and [TpA]− anions displayed perpendicular distribution that can effectively neutralize charges on the carbon surfaces. However, the [HFuA]− anion exhibited somewhat tilted configurations on the carbon electrode surfaces, contributing to their outstanding capacitive performance in electrochemical devices.
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| 32. |
- Khan, Inayat Ali, et al.
(författare)
-
Fluorine-Free Ionic Liquid-Based Electrolyte for Supercapacitors Operating at Elevated Temperatures
- 2020
-
Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 8:27, s. 10212-10221
-
Tidskriftsartikel (refereegranskat)abstract
- We synthesized tetra(n-butyl)phosphonium furoate [P4444][FuA] ionic liquid (IL) by the reaction of tetra(n-butyl)phosphonium hydroxide and 2-furoic acid using water as a solvent at room temperature. The thermal stability and phase behavior of the IL are investigated through thermogravimetry (TGA) and differential scanning calorimetry (DSC), while the ionic conductivity measurement is carried out using impedance spectroscopy. Hybrid carbon-based material composed of multi walled carbon nanotubes (MWCNTs) and activated charcoal is fabricated and used as electrodes. The effect of potential scan rate, temperature and voltage on the electrochemical performance of the capacitor is thoroughly investigated through cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). The results showed that the internal resistance and specific capacitance are highly dependent on the temperature and voltage, and a high specific capacitance of 141.4 F g−1 (5 mV s−1) from CV and 182 F g−1 (1 A g−1) from GCD at 100 °C is achieved, indicating an excellent electrochemical performance. The capacitor demonstrated 29.0 Wh kg−1 energy density and 13.3 kW kg−1 power density at 20 °C and 3 V potential, while 177 Wh kg−1 energy density and 82 kW kg−1 power density are achieved at higher temperature (100 °C). The FTIR analysis of the capacitor after electrochemical studies confirmed that no changes have occurred in the structure of the IL, indicating high electrochemical stability of the IL for supercapacitor applications in an extended temperature (−20 to 100 °C) and a wide potential range (3 V to 4.6 V).
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| 33. |
- Khan, Inayat Ali, et al.
(författare)
-
Ion Transport and Electrochemical Properties of Fluorine-Free Lithium-Ion Battery Electrolytes Derived from Biomass
- 2021
-
Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 9:23, s. 7769-7780
-
Tidskriftsartikel (refereegranskat)abstract
- Unlike conventional electrolytes, ionic liquid (IL)-based electrolytes offer higher thermal stability, acceptable ionic conductivity, and a higher electrochemical stability window (ESW), which are indispensable for the proper functioning of Li-ion batteries. In this study, fluorine-free electrolytes are prepared by mixing the lithium furan-2-carboxylate [Li(FuA)] salt with the tetra(n-butyl)phosphonium furan-2-carboxylate [(P4444)(FuA)] IL in different molar ratios. The anion of these electrolytes is produced from biomass and agricultural waste on a large scale and, therefore, this study is a step ahead toward the development of renewable electrolytes for batteries. The electrolytes are found to have Tonset higher than 568 K and acceptable ionic conductivities in a wide temperature range. The pulsed field gradient nuclear magnetic resonance (PFG-NMR) analysis has confirmed that the (FuA)− anion diffuses faster than the (P4444)+ cation in the neat (P4444)(FuA) IL; however, the anion diffusion becomes slower than cation diffusion by doping Li salt. The Li+ ion interacts strongly with the carboxylate functionality in the (FuA)− anion and diffuses slower than other ions over the whole studied temperature range. The interaction of the Li+ ion with the carboxylate group is also confirmed by 7Li NMR and Fourier transform infrared (FTIR) spectroscopy. The transference number of the Li+ ion is increased with increasing Li salt concentration. Linear sweep voltammetry (LSV) suggests lithium underpotential deposition and bulk reduction at temperatures above 313 K.
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| 34. |
- Khan, Inayat, et al.
(författare)
-
Zinc-Coordination Polymer-Derived Porous Carbon-Supported Stable PtM Electrocatalysts for Methanol Oxidation Reaction
- 2021
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Ingår i: ACS Omega. - : American Chemical Society (ACS). - 2470-1343. ; 6:10, s. 6780-6790
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Tidskriftsartikel (refereegranskat)abstract
- Porous carbon (PC) is obtained by carbonizing a zinc-coordination polymer (MOF-5) at 950 °C and PtM (M = Fe, Co, Ni, Cu, Zn) nanoparticles (NPs), which are deposited on PC using the polyol method. Structural and morphological characterizations of the synthesized materials are carried out by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HRTEM), and the porosity was determined using a N2 adsorption/desorption technique. The results revealed that PtM NPs are alloyed in the fcc phase and are well dispersed on the surface of PC. The electrochemical results show that PtM/PC 950 catalysts have higher methanol oxidation reaction (MOR) performances than commercial Pt/C (20%) catalysts. After 3000 s of chronoamperometry (CA) test, the MOR performances decreased in the order of Pt1Cu1/PC 950 > Pt1Ni1/PC 950 > Pt1Fe1/PC 950 > Pt1Zn1/PC 950 > Pt1Co1/PC 950. The high MOR activities of the synthesized catalysts are attributed to the effect of M on methanol dissociative chemisorption and improved tolerance of Pt against CO poisoning. The high specific surface area and porosity of the carbon support have an additional effect in boosting the MOR activities. Screening of the first row transition metals (d5+n, n = 1, 2, 3, 4, 5) alloyed with Pt binary catalysts for MOR shows that Pt with d8 (Ni) and d9 (Cu) transition metals, in equivalent atomic ratios, are good anode catalysts for alcohol fuel cells.
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| 35. |
- Kim, Injeong, et al.
(författare)
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Investigations into the use of Maleic Anhydride/Sodium Hypophosphite as a Wood Modification Process
- 2020
-
Ingår i: Proceedings IRG Annual Meeting 2020. - Stockholm : The International Research Group on Wood Protection.
-
Konferensbidrag (refereegranskat)abstract
- The formation of crosslinked bonds between wood constituents is believed to be an effective way to stabilize wood against wet conditions. The possibility to use maleic anhydride (MA) combined with sodium hypophosphite (SHP) as crosslinking agents was studied, using Scots pine sapwood and a model compound. The modified wood showed weight gain and bulking effect after treatment and subsequent Soxhlet extractions, which indicated penetration into the wood cell wall and reaction of the chemicals with the wood constituents. The FTIR spectra confirmed the formation of an ester bond between the wood and MA. Furthermore, a decrease of intensity of band at 1635 cm-1 indicated a reduction of the double bond between carbons in MA after further treatment with SHP, especially at 170 ̊C. Such reactions were studied using monomethyl maleate (MMM) and SHP. The 13C NMR spectra of the reaction product confirmed a reduction of the double bond between carbons. This paper outlines studies undertaken to date, along with outlining aims of ongoing and future work.
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| 36. |
- Kim, Injeong, et al.
(författare)
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Wood modification with maleic anhydride and sodium hypophosphite
- 2019
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Ingår i: Proceedings of the 20th International Symposium on Wood, Fiber and Pulping Chemistry, ISWFPC20, September 9-11, 2019, Tokyo, Japan, 4 pp.. - Tokyo : The University of Tokyo. ; , s. 1-4
-
Konferensbidrag (refereegranskat)
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| 37. |
- Loseva, Olga V., et al.
(författare)
-
Two structural types of dithiocarbamato-chlorido complexes of mercury(II): Preparation, supramolecular self-assembly, solid-state 13C and 15N NMR characterisation and thermal behaviour of pseudo-polymeric compounds of [Hg2(S2CNBu2)2Cl2] and [Hg4(S2CNiBu2)6][Hg2Cl6]
- 2022
-
Ingår i: Inorganica Chimica Acta. - : Elsevier. - 0020-1693 .- 1873-3255. ; 533
-
Tidskriftsartikel (refereegranskat)abstract
- Two new crystalline dithiocarbamato-chlorido complexes of mercury(II), [Hg2{S2CN(C4H9)2}2Cl2] (1) and [Hg4{S2CN(iso-C4H9)2}6][Hg2Cl6] (2), have been prepared and chemically identified by solution (1H, 13C) NMR and solid-state (13C, 15N) CP-MAS NMR and FT-IR spectroscopy. The crystal, molecular and supramolecular structures of these compounds were established using single-crystal X-ray diffraction (XRD) analysis. The obtained complexes reveal two principally different types of structural organisation. In the structure of the former neutral complex, there are two isomeric doubly-bridged binuclear molecules [Hg2(S2CNBu2)2Cl2] (‘A’ and ‘B’), whereas the latter compound comprises two ionic structural moieties: the tetranuclear cation [Hg4(S2CNiBu2)6]2+ and the binuclear anion [Hg2Cl6]2−. In both ionic units, pairs of iBu2Dtc or chloride ligands, which perform a bridging structural function, combine with neighbouring mercury atoms. In turn, intermolecular/interionic secondary interactions Hg···S/Hg···Cl are involved in the formation of supramolecular structures of complexes 1/2, yielding pseudo-polymeric chains of (···‘A’···‘B’···)n/(···[Hg4(S2CNiBu2)6]···[Hg2Cl6]···)n, which exhibit alternation of isomeric molecules of 1/ionic moieties of 2 along their lengths. Despite the significant structural difference between the above complexes, we established, using simultaneous thermal analysis (STA), that both exhibit very similar thermal behaviour. Moreover, during the thermal transformations of both compounds 1 and 2, the same two substances are generated: HgCl2 and HgS.
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| 38. |
- Munavirov, Bulat, et al.
(författare)
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The effect of anion architecture on the lubrication chemistry of phosphonium orthoborate ionic liquids
- 2021
-
Ingår i: Scientific Reports. - : Springer Nature. - 2045-2322. ; 11:1
-
Tidskriftsartikel (refereegranskat)abstract
- Phosphonium ionic liquids with orthoborate anions have been studied in terms of their interfacial film formation, both physisorbed and sacrificial from chemical breakdown, in sheared contacts of varying harshness. The halogen-free anion architecture was varied through (i) the heteronuclear ring size, (ii) the hybridisation of the constituent atoms, and (iii) the addition of aryl functionalities. Time of Flight-Secondary Ion Mass Spectrometry analysis revealed the extent of sacrificial tribofilm formation allowing the relative stability of the ionic liquids under tribological conditions to be determined and their breakdown mechanisms to be compared to simple thermal decomposition. Overall, ionic liquids outperformed reference oils as lubricants; in some cases, sacrificial films were formed (with anion breakdown a necessary precursor to phosphonium cation decomposition) while in other cases, a protective, self-assembly lubricant layer or hybrid film was formed. The salicylate-based anion was the most chemically stable and decomposed only slightly even under the harshest conditions. It was further found that surface topography influenced the degree of breakdown through enhanced material transport and replenishment. This work thus unveils the relationship between ionic liquid composition and structure, and the ensuing inter- and intra-molecular interactions and chemical stability, and demonstrates the intrinsic tuneability of an ionic liquid lubrication technology.
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| 39. |
- Mushtaq, Irrum, et al.
(författare)
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Engineering electroactive and biocompatible tetra(aniline)-based terpolymers with tunable intrinsic antioxidant properties in vivo
- 2020
-
Ingår i: Materials science & engineering. C, biomimetic materials, sensors and systems. - : Elsevier. - 0928-4931 .- 1873-0191. ; 108
-
Tidskriftsartikel (refereegranskat)abstract
- Under different pathological conditions, high levels of reactive oxygen species (ROS) cause substantial damage to multiple organs. To counter these ROS levels in multiple organs, we have engineered highly potent novel terpolymers. We found that combination of FDA-approved polyethylene glycol, fumaric acid moieties and electroactive tetra(aniline) by varying the content of tetra(aniline) results into a novel drug composition with biologically active tunable intrinsic antioxidant properties. To test tunable intrinsic antioxidative properties of these engineered novel terpolymers, we used alloxan to induce diabetes in rats where ROS generation is known to be higher. The systemic administration of terpolymers to the diabetic rats showed strong electroactive antioxidant behavior which normalized ROS levels, enzymatic antioxidants including superoxide dismutase, catalase, but also reduced glutathione. As a proof-of-principle, we here show TANI based novel drug composition of terpolymers with tunable intrinsic antioxidant effects confirmed in multiple organs.
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| 40. |
- Mushtaq, Irrum, et al.
(författare)
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Tunable Self-Assembled Nanostructures of Electroactive PEGylated Tetra(Aniline) Based ABA Triblock Structures in Aqueous Medium
- 2019
-
Ingår i: Frontiers in Chemistry. - : Frontiers Media S.A.. - 2296-2646. ; 7, s. 1-10
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Tidskriftsartikel (refereegranskat)abstract
- PEGylated tetra(aniline) ABA triblock structure PEG-TANI-PEG (2) consisting of tetra(aniline) (TANI) and polyethylene glycol (PEG) was synthesized by coupling the tosylated-PEG to boc-protected NH2/NH2 TANI (1) through a simple nucleophilic substitution reaction. Deprotection of 2 resulted in a leucoemeraldine base state of TANI (2-LEB), which was oxidized to stable emeraldine base (2-EB) state. 2-EB was doped with 1 M HCl to emeraldine salt (2-ES) state. FTIR, 1H and 13C NMR and UV-Vis-NIR spectroscopy, and MS (ESI) was used for structural characterization. The synthesized triblock structure exhibited good electroactivity as confirmed by CV and UV-Vis-NIR spectroscopy. Self-assembling of the triblock structure in aqueous medium was assessed by DLS, TEM, and SEM. Spherical aggregates were observed with variable sizes depicting the effect of concentration and oxidation of 2-LEB. Further, the aggregates showed acid/base sensitivity as evaluated by doping and dedoping of 2-EB with 1 M HCl and 1 M NH4OH, respectively. Future applications in drug delivery and sensors are envisaged for such tunable self-assembled nanostructures in aqueous media.
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| 41. |
- Naz, Sadia, et al.
(författare)
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One-Pot Deconstruction and Conversion of Lignocellulose Into Reducing Sugars by Pyridinium-Based Ionic Liquid–Metal Salt System
- 2020
-
Ingår i: Frontiers in Chemistry. - : Frontiers Media S.A.. - 2296-2646. ; 8
-
Tidskriftsartikel (refereegranskat)abstract
- Constantly decreasing fossil resources and exceeding energy demands are the most alarming concerns now-a-days. The only way out is to develop efficient, safe and economic biomass processing protocols that can lead towards biofuels and fine chemicals. This research is one of such consequences involving the deconstruction and conversion of wheat straw carbohydrate constituents into reducing sugars via one-pot reaction promoted by Lewis acidic pyridinium based ionic liquids (PyILs) mixed with different metal salts (MCl). Various parameters such as the type of metal salt, loading amount of metal salt, time, temperature, particle size of biomass and water content which affect the deconstruction of wheat straw have been evaluated and optimized. Among the studied IL and metal salt systems, the best results were obtained with [BMPy]+CoCl3‒. The dinitrosalicylic acid (DNS) assay was used to determine the percentage of total reducing sugars (TRS) generated during treatment of wheat straw. The deconstructed wheat straw was characterized with various analytical tools i.e. FTIR, SEM and XRD analyses. The ionic liquid‒metal salt system was recycled for subsequent treatment of wheat straw. Statistical parameters were calculated from analysis of variance (ANOVA) at 0.05 level of confidence.
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| 42. |
- Nazir, Uzma, et al.
(författare)
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Biferrocenyl Schiff bases as efficient corrosion inhibitors for an aluminium alloy in HCl solution : a combined experimental and theoretical study
- 2020
-
Ingår i: RSC Advances. - : Royal Society of Chemistry. - 2046-2069. ; 10:13, s. 7585-7599
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Tidskriftsartikel (refereegranskat)abstract
- The corrosion inhibitive capabilities of some ferrocene-based Schiff bases on aluminium alloy AA2219-T6 in acidic medium were investigated using Tafel polarization, electrochemical impedance spectroscopy (EIS), weight loss measurement, FT-IR spectroscopy and scanning electron microscopic (SEM) techniques. The influence of molecular configuration on the corrosion inhibition behavior has been explored by quantum chemical calculation. Ferrocenyl Schiff bases 4,4′-((((ethane-1,2-diylbis(oxy))bis(4,1-phenylene))bis(methaneylylidene))bis(azaneylylidene))bisferrocene (Fcua), 4,4′-((((ethane-1,2-diylbis(oxy))bis(2-methoxy-1,4-phenylene))bis(methaneylylidene))bis(azaneylylidene))bisferrocene (Fcub) and 4,4′-((((ethane-1,2-diylbis(oxy))bis(2-ethoxy-1,4-phenylene))bis(methaneylylidene))bis(azaneylylidene))bisferrocene (Fcuc) have been synthesized and characterized by FT-IR, 1H and 13C NMR spectroscopic studies. These compounds showed a substantial corrosion inhibition against aluminium alloy in 0.1 M of HCl at 298 K. Fcub and Fcuc showed better anticorrosion efficiency as compared with Fcua due to the electron donating methoxy and ethoxy group substitutions, respectively. Polarization curves also indicated that the studied biferrocenyl Schiff bases were mixed type anticorrosive materials. The inhibition of the aluminium alloy surface by biferrocenyl Schiff bases was evidenced through scanning electron microscopy (SEM) studies. Semi-empirical quantum mechanical studies revealed a correlation between corrosion inhibition efficiency and structural functionalities.
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| 43. |
- Nazir, Uzma, et al.
(författare)
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Experimental and theoretical insights into the corrosion inhibition activity of novel Schiff bases for aluminum alloy in acidic medium
- 2019
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Ingår i: RSC Advances. - : Royal Society of Chemistry. - 2046-2069. ; 9:62, s. 36455-36470
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Tidskriftsartikel (refereegranskat)abstract
- Three novel Schiff bases, namely N-(4-((4-((phenylimino)methyl)phenoxy)methoxy)benzylidene)benzenamine (UA), N-(3-methoxy-4-((2-methoxy-4-((phenylimino)methyl)phenoxy)methoxy)benzylidene)benzenamine (UB), and N-(3-ethyl-4-((2-ethyl-4-((phenylimino)methyl)phenoxy)methoxy)benzylidene)benzenamine (UC), were synthesized and their structures were elucidated through diverse spectroscopic techniques such as FT-IR, GC-MS, 1H NMR and 13C NMR. The corrosion inhibition effect of these Schiff bases on aluminum alloy AA2219-T6 in acidic medium was explored using weight loss, Tafel polarization, and electrochemical impedance spectroscopy. Theoretical quantum chemical calculations using density functional theory were employed to determine the adsorption site. It was found that inhibition efficiencies increase with an increase in the inhibitor concentration. Tafel plots showed that these Schiff bases function as mixed inhibitors. Adsorption of the Schiff bases on aluminum followed the Langmuir adsorption isotherm and the value of showed a dominant chemical mechanism. FT-IR and SEM techniques were used to investigate the surface morphology. The compounds showed a substantial corrosion inhibition for aluminum alloy in 0.1 M HCl at 298 K. UB and UC exhibited superior anticorrosion efficiency compared to UA originating from the electron-donating methoxy and ethoxy group substitutions, respectively. There was found to be good correlation between molecular structure and inhibition efficiencies.
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| 44. |
- Qiu, Xiuhua, et al.
(författare)
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Probing the nanofriction of non-halogenated phosphonium-based ionic liquid additives in glycol ether oil on titanium surface
- 2022
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Ingår i: Friction. - : Springer. - 2223-7690 .- 2223-7704. ; 10:2, s. 268-281
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Tidskriftsartikel (refereegranskat)abstract
- The nanofrictional behavior of non-halogentated phosphonium-based ionic liquids (ILs) mixed with diethylene glycol dibutyl ether in the molar ratios of 1:10 and 1:70 was investigated on the titanium (Ti) substrate using atomic force microscopy (AFM). A significant reduction is observed in the friction coefficient μ for the IL-oil mixtures with a higher IL concentration (1:10, μ ∼ 0.05), compared to that for the lower concentration 1:70 (μ ∼ 0.1). AFM approaching force-distance curves and number density profiles for IL-oil mixtures with a higher concentration revealed that the IL preferred to accumulate at the surface forming IL-rich layered structures. The ordered IL-rich layers formed on the titanium surface facilitated the reduction of the nanoscale friction by preventing direct surface-to-surface contact. However, the ordered IL layers disappeared in the case of lower concentration, resulting in an incomplete boundary layers, because the ions were displaced by molecules of the oil during sliding and revealed to be less efficient in friction reduction.
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| 45. |
- Reddy, Akepati Bhaskar, Dr. 1990-, et al.
(författare)
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Ionic liquids enhance electrical conductivity of greases: an impedance spectroscopy study
- 2024
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Ingår i: Colloids and Surfaces A. - : Elsevier. - 0927-7757 .- 1873-4359. ; 683
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Tidskriftsartikel (refereegranskat)abstract
- Ionic liquids (ILs) have emerged as viable solutions for developing new-age lubricants, both as neat lubricants and lubricant additives. Enabled by the presence of discrete ions, ILs have the possibility to render electrically conductive lubricants, which is a feasible strategy for developing lubricant systems compatible with modern e-drive conditions. However, this requires the characterization of the electrical properties of lubricants, which is a bottleneck for developing electrically conductive greases, given their complex architecture. This work introduces an electrochemical impedance spectroscopy measurement methodology to evaluate grease samples' electrical properties. Compared to the commonly used conductivity meters, this method, through its multi-frequency alternating current (AC) impedance approach, can effectively distinguish the individual contributions of the bulk and the sample-electrode interface to the measured electrical response. Impedance spectra of grease samples are obtained using an electrochemical cell with parallel plate electrodes, mounted on a temperature-controlled cell stand and coupled with a potentiostat. The grease's bulk conductivity is extracted by fitting the impedance data to relevant equivalent electrical circuits. The bulk conductivity of lithium complex grease doped with ILs is evaluated and compared to greases with conventional conductivity additives (copper powder and conductive carbon black). The analysis of temperature-dependent conductivity reveals the rather different conductivity mechanisms for different additives. For greases doped with ILs, a comparison against the electrical conductivity of neat ILs reveals that, in addition to the ion dissociation, the interaction of the ions with the different grease components (base oil, thickener) is crucial in defining the grease conductivity.
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| 46. |
- Shah, Faiz Ullah, 1981-, et al.
(författare)
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Comparing the thermal and electrochemical stabilities of two structurally similar ionic liquids
- 2020
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Ingår i: Molecules. - : MDPI AG. - 1420-3049 .- 1420-3049 .- 1431-5157. ; 25:10
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Tidskriftsartikel (refereegranskat)abstract
- Here we focus on the thermal and variable temperature electrochemical stabilities of two ionic liquids (ILs) having a common tributyloctyl phosphonium cation [P4,4,4,8]+ and two different orthoborate anions: bis(mandelato)borate [BMB]− and bis(salicylato)borate [BScB]−. The thermogravimetric analysis data suggest that [P4,4,4,8][BScB] is thermally more stable than [P4,4,4,8][BMB] in both nitrogen atmosphere and air, while the impedance spectroscopy reveals that [P4,4,4,8][BScB] has higher ionic conductivity than [P4,4,4,8][BMB] over the whole studied temperature range. In contrast, the electrochemical studies confirm that [P4,4,4,8][BMB] is more stable and exhibits a wider electrochemical stability window (ESW) on a glassy carbon electrode surface as compared to [P4,4,4,8][BScB]. A continuous decrease in the ESWs of both ILs is observed as a function of operation temperature.
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| 47. |
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| 48. |
- Shah, Faiz Ullah, 1981-, et al.
(författare)
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Interfacial Behavior of Orthoborate Ionic Liquids at Inorganic Oxide Surfaces Probed by NMR, IR, and Raman Spectroscopy
- 2018
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 122:34, s. 19687-19698
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Tidskriftsartikel (refereegranskat)abstract
- Absorption modes and the reactivity of nonhalogenated ionic liquids (ILs) at inorganic oxide surfaces of γ-Al2O3, MgO, and SiO2 particles were characterized using multinuclear (11B, 31P, and 29Si) solid-state magic-angle-spinning NMR, FTIR, and Raman spectroscopy. ILs are composed of the trihexyl(tetradecyl)phosphonium cation, [P6,6,6,14]+, and bis(mandelato)borate, [BMB]-, or bis(salicylato)borate, [BScB]-, anions. Spectroscopic measurements were performed on room-temperature (298 K) samples and samples exposed to 15 h at 373 K. The single-pulse 11B NMR data of heated [P6,6,6,14][BMB] mixed with the inorganic oxides showed a significant change in the spectra of the anion for all three oxides. In contrast, no such spectral changes were detected for heated [P6,6,6,14][BScB] mixed with the inorganic oxides. 31P MAS NMR data for the IL/metal oxide systems revealed interactions between [P6,6,6,14]+ and the surfaces of oxides. A significant intensity of 31P CP-MAS NMR signals indicated a low mobility of cations in these systems. The existence of strongly adhered surface layers of ILs on SiO2 particles was also confirmed by 1H-29Si CP-MAS NMR spectroscopy. FTIR and Raman spectroscopic data revealed strong interactions between the anions and the inorganic surfaces, and there is a strong correlation with the data obtained from NMR spectroscopy. Although their chemical structures are rather similar, the [BScB]- anion is more stable than the [BMB]- anion at the inorganic oxide surfaces.
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| 49. |
- Shah, Faiz Ullah, 1981-, et al.
(författare)
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Structural and Ion Dynamics in Fluorine-Free Oligoether Carboxylate Ionic Liquid-Based Electrolytes
- 2020
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-5207 .- 1520-6106. ; 124:43, s. 9690-9700
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Tidskriftsartikel (refereegranskat)abstract
- Here, we investigate the physicochemical and electrochemical properties of fluorine-free ionic liquid (IL)-based electrolytes with two different cations, tetrabutylphosphonium, (P-4,4,4,(4))(+), and tetrabutylammonium, (N-4,N-4,N-4,N-4)(+), coupled to a new anion, 2-[2-(2-methoxyethoxy)ethoxylacetate anion (MEEA), for both neat and (P-4,P-4,P-4,P-4) (MEEA)(-), also doped with 10-40 mol % of Li(MEEA). We find relatively weaker cation-anion interactions in (P-4,P-4,P-4,P-4)(MEEA) than in (N-4,N-4,N-4,N-4)(MEEA), and for both ILs, the structural flexibility of the oligoether functionality in the anion results in low glass transition temperatures, also for the electrolytes made. The pulsed field gradient nuclear magnetic resonance (PFG NMR) data suggest faster diffusion of the (MEEA)(-) anion than (P-4,P-4,P-4,P-4)(+) cation in the neat IL, but the addition of a Li salt results in slightly lower mobility of the former than the latter and lower ionic conductivity. This agrees with the combined Li-7 NMR and attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy data, which unambiguously reveal preferential interactions between the lithium cations and the carboxylate groups of the IL anions, which also increased as a function of the lithium salt concentration. In total, these systems provide a stepping stone for further design of fluorine-free and low glass transition temperature IL-based electrolytes and also stress how crucial it is to control the strength of ion-ion interactions.
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| 50. |
- Shah, Faiz Ullah, 1981-, et al.
(författare)
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Transport and Association of Ions in Lithium Battery Electrolytes Based on Glycol Ether Mixed with Halogen-Free Orthoborate Ionic Liquid
- 2017
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Ingår i: Scientific Reports. - : Nature Publishing Group. - 2045-2322. ; 7
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Tidskriftsartikel (refereegranskat)abstract
- Ion transport behaviour of halogen-free hybrid electrolytes for lithium-ion batteries based on phosphonium bis(salicylato)borate [P4,4,4,8][BScB] ionic liquid mixed with diethylene glycol dibutyl ether (DEGDBE) is investigated. The Li[BScB] salt is dissolved at different concentrations in the range from 0.15 mol kg−1 to 1.0 mol kg−1 in a mixture of [P4,4,4,8][BScB] and DEGDBE in 1:5 molar ratio. The ion transport properties of the resulting electrolytes are investigated using viscosity, electrical impedance spectroscopy and pulsed-Field Gradient (PFG) NMR. The apparent transfer numbers of ions are calculated from the diffusion coefficients measured by using PFG NMR. PFG NMR data suggested ion association upon addition of Li salt to the [P4,4,4,8][BScB] in DEGDBE solution. This is further confirmed by liquid state 7Li and 11B NMR, and FTIR spectroscopic techniques, which suggest strong interactions between the lithium cation and oxygen atoms of the [BScB]− anion in the hybrid electrolytes.
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