Electrochemical synthesis of polypyrrole in ionic liquids

Electrochemical synthesis of inherently conducting polymers such as polypyrrole is traditionally performed in a molecular solvent/electrolyte system such acetonitrile/lithium perchlorate. We report the use of ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) amide and N,N-butylmethylpyrrolidinium bis(trifluoromethanesulfonyl) amide, both as the growth medium and as an electrolyte for the electrochemical cycling of polypyrrole films. Use of the ionic liquid as the growth medium results in significantly altered film morphologies and improved electrochemical activities.     

Electrochemical synthesis of poly(p-phenylene) and poly(p-phenylene)/TiO2 nanowires in an ionic liquid

This study shows for the first time that poly(p-phenylene) (PPP) nanowires can be easily obtained by electrochemical synthesis at room temperature. The method involves the template assisted electropolymerization of benzene in the air and water stable ionic liquid 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIm]FAP). Track-etched polycarbonate membranes (PC) with an average pore diameter of 90 nm were used as templates. Dense and highly flexible bundles of PPP nanowires with a high aspect ratio (>160) were easily obtained by this method. In addition, we present here our first results to obtain PPP/TiO₂ nanowires by the combination of a sol–gel technique with electropolymerization. HR-SEM, TEM and EDX were used for the structural characterization of the nanowires.     

Evidence of redox interactions between polypyrrole and Fe3O4 in polypyrrole-Fe3O4 composite films

The electrical properties of conducting polymers make them useful materials in a wide number of technological applications. In the last decade, an important effect on the properties of the conducting polymer when iron oxides particles are incorporated into the conductive matrix was shown. In the present study, films of polypyrrole were synthesized in the presence of magnetite particles. The effect of the magnetite particles on the structure of the polymer matrix was determined using Raman spectroscopy. Mass variations at different concentrations of Fe₃O₄ incorporated into the conducting matrix were also measured by means of quartz crystal microbalance. Additionally, the changes in the resistance of the films were evaluated over time by electrochemical impedance spectroscopy in solid state. These results show that the magnetite incorporation decreases polymeric film resistance and Raman experiments have evidenced that the incorporation of magnetite into polymeric matrix not only stabilizes the polaronic form of the polypyrrole, but also preserves the polymer from further oxidation.     

Fixation and conversion of CO2 using ionic liquids

Ionic liquids (ILs), a kind of novel green media composed entirely of cations and anions, have recently attracted considerable attention due to their unique properties such as non-volatility, tunable polarity, high stability and so on. In this work, the latest progress on the fixation and conversion of carbon dioxide (CO₂) using ILs as absorbents, catalysts or promoters has been summarized. The absorption performance of conventional ILs and task-specific ILs was systematically investigated, the conversion of CO₂ with epoxides, propargyl alcohols and amines using ILs was critically evaluated, and the significant advantages in the fixation and conversion of CO₂ using the ILs were demonstrated compared to the conventional absorbents and the catalytic systems without ILs. This research progress may finally lead to building of an in situ fixation–conversion process of CO₂ with ILs. If so, we are near an epoch of the fixation and utilization of CO₂, although there is obviously a long way to go for us to achieve such a goal.     

Fluorescence study of film formation from PS/Al2O3 nanocomposites

Steady state fluorescence (SSF) and UV–vis (UVV) techniques were used to study the film formation behavior of pyrene (P) labeled polystyrene (PS) latex and Al₂O₃ (PS/Al₂O₃) composites depending on PS particles size and Al₂O₃ content. The close-packed arrays of PS spheres (SmPS: 203 nm; LgPS: 382 nm) templates on clean glass substrates were covered with various layers of Al₂O₃ by dip-coating method. Two different film series (SmPS/Al₂O₃ and LgPS/Al₂O₃) were prepared in various Al₂O₃ layer content. The film formation behavior of these composites were studied by annealing them at a temperature range of 100–250 °C and monitoring the scattered light intensity (I_sc), fluorescence intensity (I_P) from P and transmitted light intensity (I_tr) through the films after each annealing step. Optical results indicate that classical latex film formation was occurred for all Al₂O₃ content films and film formation process was unaffected by the Al₂O₃ content for both film series. Extraction of PS template produced highly ordered porous structures for high Al₂O₃ content in both film series. SEM images showed that the pore size and porosity could be easily tailored by varying the PS particle size and the Al₂O₃ content.     

Synthesis of novel sunflower-like silica/polypyrrole nanocomposites via self-assembly polymerization

Novel sunflower-like organic-inorganic composites consisting of spherical silica and smaller conductive polypyrrole particles were successfully prepared through an in situ self-assembly polymerization process by choosing chitosan as a modifying agent of silica surface. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that on the surface of individual silica particle polypyrrole nanoparticles were anchored perfectly. The sunflower-like silica-polypyrrole composites exhibited conductivity of 8 S cm⁻¹ and colloid stability because of the special surface morphology. Adsorbed chitosan chain may play a dual-role of both providing the active sites for formation of the polypyrrole particles on silica and acting as a stabilizer of the silica-polypyrrole particles. Hydrogen-bonding interaction between the acetylamino group of chitosan and hydrogen atom on nitrogen of polypyrrole is a determining parameter in the former case.     

Hydrothermal synthesis and characterization of In2O3-ZnGa2O4 nanocomposites and their application in IGZO ceramics

Poly-crystalline In₂O₃-ZnGa₂O₄ nanocomposites were successfully synthesized by hydrothermal method with a mixed solution of In, Ga and Zn nitrates with equal mole ratio (In: Ga: Zn=1:1:1) and the ammonia was used as the precipitant. The effects of hydrothermal temperature and pH value of the mixed solution on the properties of the nanocomposites were investigated. The microstructure of the prepared In₂O₃-ZnGa₂O₄ nanocomposites was characterized by SEM and TEM, respectively. The growth mechanisms of In₂O₃-ZnGa₂O₄ nanocomposites were also preliminarily discussed in this study. Results reveal that the IGZO ceramics prepared by In₂O₃-ZnGa₂O₄ nanocomposites own a high relative density of 99.5% and low resistivity of 1.2?mΩ·cm, which can be applied to the preparation of IGZO thin film with superior performance.     

Solubility of neutral and charged polymers in ionic liquids studied by laser light scattering

The solubility and chain conformation of different types of homopolymers in low viscosity ionic liquids (ILs), 1-allyl-3-methylimidazolium chloride ([AMIM][Cl]) at 50 °C and 1-butyl-3-methylimidazolium formate ([BMIM][COOH]) at 25 °C, were studied by laser light scattering (LLS). For neutral polymers, such as polyvinyl alcohol and polysulfonamide, aggregation occurred in all the cases except for polyvinyl alcohol in [BMIM][COOH]. For negative polyelectrolytes, such as DNA and polystyrene sulfonate, single chain conformation was observed. However, the hydrodynamic radius of both polymers was much smaller than that in good solvents, suggesting that the chains were condensed. Cellulose was soluble in [AMIM][Cl], and non-diffusive mode was observed by dynamic light scattering. Zeta potential analysis indicated that cellulose exhibited the feature of polyelectrolyte. The solubility of homopolymers could be qualitatively explained by treating polymer/IL as a ternary system: polymer, cation, and anion. It was the mutual interactions determined the solubility and conformation of polymers in ILs.     

Magnetic hydroxyapatite-encapsulated γ-Fe2O3 nanoparticles functionalized with basic ionic liquids for aqueous Knoevenagel condensation

Hydroxyapatite-encapsulated γ-Fe₂O₃ nanoparticles functionalized with diethyl aliphatic amine basic ionic liquids were synthesized and used as efficient magnetic catalysts for aqueous Knoevenagel condensation reactions. Quantitative conversion of the reactants was achieved under mild conditions; recycle of the catalyst, through convenient magnetic decantation, shows non-significant loss in activity. In comparison with the controlled experiments catalyzed by homogeneous basic ionic liquids and the basic ionic liquid-modified polystyrene resin, the excellent performance of the magnetic catalyst was attributed to the cooperativity between the base sites generated by framework HAP and the supported basic ionic liquids.     

Synthesis and physical property characterisation of phosphonium ionic liquids based on P(O)2(OR)2 and P(O)2(R)2 anions with potential application for corrosion mitigation of magnesium alloys

Phosphonium cation based ionic liquids (ILs) have become of interest due to their unique chemical and electrochemical stability as well as their promising tribological properties. At the same time, interest has also grown in the use of phosphate and phosphinate based ionic liquids for corrosion protection of reactive metals. In this work we describe the synthesis and characterization of six novel ionic liquids based on the tetraalkylphosponium cation coupled with organophosphate and organophosphinate anions and their sulfur analogues. The conductivity and viscosity of these ILs has been measured and discussed in terms of the nature of the interactions, effect of anion basicity and the extent of ionic character. The reaction of the IL with a ZE41 magnesium aerospace alloy surface is also demonstrated.     

Purification of ionic liquids by supercritical CO2 monitored by infrared spectroscopy

Transmission infrared and Attenuated Total Reflection (ATR) in situ infrared spectroscopies were combined for the time-resolved monitoring of both liquid and supercritical phases during extraction of water and other impurities from ionic liquids with supercritical carbon dioxide (scCO₂). Cleaning and drying by scCO₂ at 100 bar and 40 °C proved to be efficient for all ionic liquids tested, including 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), and 1-butyl-3-methylimidazolium trifluoromethansulfonate ([bmim][TfO] or [bmim] triflate). Despite the moderate solubility of water in scCO₂ compared to other classical solvents, the amount of water decreased continuously during the drying. The extraction could be followed by simple transmission IR spectroscopy of the supercritical phase. During the extraction, organic impurities and water were removed rapidly from the ionic liquid phase as scCO₂ improved the transport properties in the ionic liquids.     

Electropolymerization of high quality electrochromic poly(3-alkyl-thiophene)s via a room temperature ionic liquid

Electrochemical polymerization in a room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF₆), has been used to prepare electrochromic poly(3-methylthiophene) (PMeT) and its more attractive derivatives: poly(3-hexylthiophene) (PHexT) and poly(3-octylthiophene) (POcT). Spectroelectrochemistry and electrochromic properties of the resulting polymers were characterized using various experiment techniques in [BMIM]PF₆/CH₃CN (1:1, v/v) solution. The thin films were bright red, orange red and orange yellow at its fully reduced state for PMeT, PHexT and POcT, respectively. After oxidization of these undoped polymers, the films underwent reversible change to the bright blue, blue or black blue form. These poly(3-alkylthiophene)s (PMeT, PHexT and POcT) films exhibit high chromatic contrast (46, 45 or 39%), comparative switching times (1.1, 1.4 or 1.9 s), great electrochromic efficiency (250, 220 and 230 cm² C⁻¹) and long-term switching stability. High quality electrochromic polymers were provided for the use of commercially available thiophene monomers, avoiding the use of other custom synthesized monomers.     

Hydrogen bioelectrooxidation in ionic liquids: From cytochrome c3 redox behavior to hydrogenase activity

Electrochemistry of polyheme bacterial cytochrome c₃ and catalytic oxidation of hydrogen by two different bacterial [NiFe] hydrogenases were investigated for the first time in pure room-temperature ionic liquids (RTILs) as electrolyte. Direct electrochemical response of Desulfovibrio vulgaris Hildenborough cytochrome c₃ (DvH cytc₃) adsorbed at a pyrolytic graphite (PG) electrode was observed in the RTILs used in this work: 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4), 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF4) and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EmimNTf2). The electrochemical signal differed however from that obtained in aqueous buffer, and depended on the type of RTIL. UV–vis measurements as well as transfer experiments from aqueous buffer to RTILs or RTILs to aqueous buffer strongly suggested that the protein was not denatured in the presence of RTILs. EmimNTf2, as a hydrophobic non-water-miscible RTIL, was demonstrated to stabilize the native form of DvH cytc₃. Moreover it allowed an amount of electroactive DvH cytc₃ 30-fold higher than observed in aqueous buffer. Catalytic oxidation of H₂ via Desulfovibrio fructosovorans [NiFe] hydrogenase (Df Hase) mediated by DvH cytc₃ failed however. Further investigation suggested that Df Hase could be inhibited in the presence of RTILs. Reasons for such an inhibition were explored, including the blocking up of the substrate channels. By using hyperthermophilic [NiFe] membrane-bound hydrogenase from Aquifex aeolicus (Aa Hase) an efficient direct catalytic oxidation process was obtained in mixed aqueous buffer/RTILs electrolytes, although direct H₂ oxidation was not observed in pure RTIL. Chronoamperometric experiments showed that Aa Hase could afford 80% RTILs in aqueous buffer, thus giving the opportunity of future electrolytes with uncommon and variable properties for biofuel cell design.     

Polymeric ionic liquids: Broadening the properties and applications of polyelectrolytes

The introduction of new ionic moieties, cations and anions, is extending the properties and classical applications of polyelectrolytes. These new polyelectrolytes are being named polymeric ionic liquids (PILs) in analogy to their monomeric constituents (i.e. cations such as imidazolium, pyridinium, pyrrolidonium and anions such as hexafluorophosphate, triflates, amidotriflates). This is giving rise to a new family of functional polymers with particular properties and new applications. The first part of this review will focus on the synthetic aspects of PILs and the main aspects related to their physico-chemical properties. In the second part we will review the new technological applications of these polymers such as polymer electrolytes in electrochemical devices, building blocks in materials science, nanocomposites, gas membranes, innovative anion sensitive materials, smart surfaces, and a countless set of applications in different fields such as energy, environment, optoelectronics, analytical chemistry, biotechnology or catalysis.     

H2 sorption in HCl-treated polyaniline and polypyrrole

Hydrogen sorption in conducting polymers was investigated in order to determine their potential as hydrogen storage media. The conducting polymers, polyaniline and polypyrrole, were treated with an acid, which resulted in an exceptionally high hydrogen sorption, 6 and 8 wt% at room temperature and under 9.3 MPa. Both the molecular effect and electrical effects by the conducting polymers appear to play an important role in hydrogen sorption. This paper presents the preliminary results of hydrogen sorption in a conducting polymer along with its characterization by XRD, scanning electron microscopy, TGA, and conductivity measurement using a four-probe method. A possible mechanism for the extraordinarily high hydrogen storage is suggested.     

Coloring ionic trapping states in WO3 and Nb2O5 electrochromic materials

Complex electro-optical analysis is a very useful approach to separate different kinetic processes that occur during ionic insertion reactions in electrochromic oxide materials. In this paper, we use this type of combined technique to investigate ionic and optical changes in different oxide host systems, i.e., in two oxide hosts, specifically WO₃ and Nb₂O₅. A comparison of their electro-optical responses revealed the presence of an ionic trapping contribution to the kinetics of the coloring sites, which was named here as coloring ionic trapping state. As expected, this coloring trapping process is slower in Nb₂O₅ since the reduction potential of Nb₂O₅ is more negative (more energy is needed for a higher degree of coloration). A phenomenological solid-state model that encompasses homogeneous charge transfer and valence trapping was proposed to explain the coloring ionic trapping process. Basically the model is able to explain how ionic dynamics at low frequency region, i.e., the slower kinetic step, controls the coloring kinetics, i.e., how it is capable to regulate the coloring rates.Optical transient analyses demonstrated the possibility of the presence of more than one coloring ionic trap, indicating the complexity of the processes involved in coloration phenomenon in metal oxide host systems.     

XANES study of polyaniline-V2O5 and sulfonated polyaniline-V2O5 nanocomposites

In this work, two materials for secondary lithium battery cathodes formed by polyaniline-V₂O₅ and sulfonated polyaniline-V₂O₅, which have a higher charge capacity than the V₂O₅ xerogel, were synthesized. X-ray absorption and Fourier transform infrared spectroscopies were employed to analyze the short-range interactions in these materials. Based on these experiments, it was possible to observe significant differences in the symmetry of the VO₅ units, and this was attributed to the intimate contact between V₂O₅ and the polymers, and to some flexibility of the VO₅ square pyramids due to the low range order of the nanocomposites.     

Thermal shock of ground and polished alumina and Al2O3/SiC nanocomposites

The thermal shock behaviour of sintered alumina and alumina/SiC nanocomposites with 1, 2.5 and 5 vol.% SiC was studied. The thermal shock testing was carried out by means of quenching into water from high temperatures (ΔT in the range 0–750 °C). Both single shocks and repeated shocks were used. The damage introduced by thermal shock was characterised by degradation of strength in four-point bending and by changes in Young's modulus. The effects of the surface finish of the test specimens (either ground or highly polished surfaces) on the thermal shock resistance were also studied. In both alumina and nanocomposite materials, specimens with ground surfaces showed a better resistance to thermal shocks than specimens with polished surfaces. However, the resistance of the nanocomposite material to single and repeated thermal shocks was no better than that of the pure alumina.     

[BMIM]BF4 ionic liquids as effective inhibitor for carbon steel in alkaline chloride solution

The inhibition action of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF₄) ionic liquids towards carbon steel corrosion in alkaline chloride solution was investigated by electrochemical measurements. The morphology of the surface was examined by atomic force microscopy (AFM), and the surface composition was evaluated via X-ray photoelectron spectroscopy (XPS) as well in order to verify the presence of inhibitor on the carbon steel surface. The results showed that the compound effectively suppressed both cathodic and anodic processes of carbon steel corrosion in alkaline solution by multi-center adsorption on carbon steel surface according to Langmuir adsorption isotherm, and acted as a mixed type inhibitor. The inhibition mechanism was proposed based on the viewpoint of complex physic-chemical interactions between the cationic inhibitor molecule and the carbon steel surface.     

High pressure CO2 solubility in N-methyl-2-hydroxyethylammonium protic ionic liquids

The use of ionic liquids for CO₂ capture and natural gas sweetening is being object of intense research. Within the enormous group of existing ionic liquids, those based on conjugate bases of carboxylic acids seem to be particularly promising. This work addresses the study of the high pressure CO₂ solubility (up to 80 MPa) in two protic ionic liquids, N-methyl-2-hydroxyethylammonium formate and N-methyl-2-hydroxyethylammonium acetate, in a wide range of temperatures (293-353 K). A thermodynamic model based on the Peng-Robinson equation of state with the Wong-Sandler mixing rule, using the NRTL model for the activity coefficients, was here adopted to describe and evaluate the thermodynamic consistency of the experimental data. Furthermore, the study of a ternary mixture of CO₂ + CH₄ + N-methyl-2-hydroxyethylammonium acetate was investigated showing a high selectivity from the IL towards these solutes.