Organic acid doped polyaniline derivatives

Soluble poly (o-toluidine) (POT), poly(o-anisidine) (PAs) and poly (o-chloroaniline) (PCAn) were doped with camphorsulfonic acid (CSA). The conductivity and UV-Vis spectra of the CSA-doped POT, PAs and PCAn were studied. These properties were found to be dependent on the solvent used. The cast films from m-cresol solution exhibit more effective doping and higher conductivity.

Poly(2,5-bibenzimidazole) Membranes: Physico-Chemical Characterization Focused on Fuel Cell Applications

Membranes of Poly(2,5-benzimidazole) (ABPBI), prepared by polycondensation in polyphosphoric acid, were characterized from the fuel cell application point of view: mechanical properties of the membranes for different acid doping levels, thermal stability, permeability for the different gases/vapors susceptible of use in the cell (hydrogen, oxygen, methanol and ethanol), electro-osmotic water drag coefficient, oxidation stability to hydroxyl radicals, phosphoric acid leaching rate and, finally, in-plane membrane conductivity. ABPBI membranes presented an excellent thermal stability, above 500 degrees C in oxygen, suitable mechanical properties for high phosphoric acid doping levels, a low methanol and ethanol limiting permeation currents, and oxygen permeability compared to Nafion membranes, and a low phosphoric acid leaching rate when exposed to water vapor. On the contrary, hydrogen permeation current was higher than that of Nafion, and the chemical stability was very limited. Membrane conductivity achieved 0.07 S cm(-1) after equilibration with a humid environment. Fuel cell tests showed reasonable good performances, with a maximum power peak of 170 mW cm(-2) for H-2/air at 170 degrees C operating under a humidified hydrogen stream, 39.9 mW cm(-2) for CH3OH/O-2 at 200 degrees C for a methanol/water weight ratio of 1: 2, and 31.5 mW cm(-2) for CH3CH2OH/O-2 at the same conditions than for methanol. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.014207jes] All rights reserved.

Computational modeling of intermediate temperature proton exchange membrane (PEM) fuel cells

A two-phase three-dimensional computational model of an intermediate temperature (120--190°C) proton exchange membrane (PEM) fuel cell is presented. This represents the first attempt to model PEM fuel cells employing intermediate temperature membranes, in this case, phosphoric acid doped polybenzimidazole (PBI). To date, mathematical modeling of PEM fuel cells has been restricted to low temperature operation, especially to those employing Nafion ® membranes; while research on PBI as an intermediate temperature membrane has been solely at the experimental level. This work is an advancement in the state of the art of both these fields of research. With a growing trend toward higher temperature operation of PEM fuel cells, mathematical modeling of such systems is necessary to help hasten the development of the technology and highlight areas where research should be focused.^ This mathematical model accounted for all the major transport and polarization processes occurring inside the fuel cell, including the two phase phenomenon of gas dissolution in the polymer electrolyte. Results were presented for polarization performance, flux distributions, concentration variations in both the gaseous and aqueous phases, and temperature variations for various heat management strategies. The model predictions matched well with published experimental data, and were self-consistent.^ The major finding of this research was that, due to the transport limitations imposed by the use of phosphoric acid as a doping agent, namely low solubility and diffusivity of dissolved gases and anion adsorption onto catalyst sites, the catalyst utilization is very low (∼1--2%). Significant cost savings were predicted with the use of advanced catalyst deposition techniques that would greatly reduce the eventual thickness of the catalyst layer, and subsequently improve catalyst utilization. The model also predicted that an increase in power output in the order of 50% is expected if alternative doping agents to phosphoric acid can be found, which afford better transport properties of dissolved gases, reduced anion adsorption onto catalyst sites, and which maintain stability and conductive properties at elevated temperatures.^

Interaction of N-methylpyrrolidone with doped polyaniline

The interaction of N-methyl-2-pyrrolidone (NMP) and organic acid doped polyaniline (PAn) is studied by UV-Vis-NIR spectroscopy. A dedoping effect is observed when the doped PAn solution is extremely diluted by NMP. This effect is due to a strong interaction between NMP and the dopant acid. The competition between NMP and PAn is responsible for the poor conformation of doped polyaniline in NMP solution and the poor conductivity of the film cast from this solution.

Phenylene vinylene-based electroluminescent polymers with electron transport block in the main chain

We report a new route for the design of soluble phenylene vinylene (PV) based electroluminescent polymers bearing electron-deficient oxadizole (OXD) and triazole (TZ) moieties in the main chains with the aryloxy linkage. Both series of the PV-based polymers were prepared by Wittig reaction. By properly adjusting the OXD and/or TZ content through copolymerization, we can achieve an enhanced balance of hole- and electron injections, such that the device efficiency is significantly improved. Light-emitting diodes fabricated from P1, P2, P3, P4, P5, P6, and P7 with the configuration of Indium-Tin Oxide (ITO)/Poly (styrene sulfonic acid) doped poly (ethylenedioxythiophene) (PEDOT)/polymer/Ca/Al, emit bright green light with the maximum peak around 500 nm. For the device using the optimal polymer (P4) as emitting layer, a maximum brightness of 1300 cd/m(2) at 20 V and a maximum luminance efficiency of 0.325 cd/A can be obtained.

Trimethoxymethane as an alternative fuel for a direct oxidation PBI polymer electrolyte fuel cell

The oxidation of trimethoxymethane (TMM) (trimethyl orthoformate) in a direct oxidation PBI fuel cell was examined by on-line mass spectroscopy and on-line FTIR spectroscopy. The results show that TMM was almost completely hydrolyzed in a direct oxidation fuel cell which employs an acid doped polymer electrolyte to form a mixture of methylformate, methanol and formic acid. It also found that TMM was hydrolyzed in the presence of water at 120°C even without acidic catalyst. The anode performance improves in the sequence of methanol, TMM, formic acid/methanol, and methylformate solutions. Since formic acid is electrochemically more active than methanol, these results suggest that formic acid is probably a key factor for the improvement of the anode performance by using TMM instead of methanol under these conditions. © 1998 Elsevier Science Ltd. All rights reserved.

A selective conductive polymer-based sensor for volatile halogenated organic compounds (VHOC)

A novel poly(p-xylylene), PPX, derivative bearing alkoxyphenyl side groups was electrochemically synthesized in 87% yield. The polymer, poly(4`-hexyloxy-2,5-biphenyleneethylene) (PHBPE), presented a fraction (92%) soluble in common organic solvents. It showed to be thermally resistant up to 185 degrees C. UV-vis analysis revealed an E-gap of 3.5 eV Gas sensors made from thin films of 10-camphorsulfonic acid-doped PHBPE deposited on interdigitated electrodes exhibited significant changes in electrical conductance upon exposure to five VHOCs: 1,2-dichloroethane, bromochloromethane, trichloromethane, dichloromethane and tetrachloromethane. The conductance decreased after exposure to tetrachloromethane and increased after exposure to all the other VHOCs. Three-dimensional plots of relative response versus time of half response versus time of half recovery showed good discrimination between the five VHOCs tested. (c) 2008 Elsevier B.V. All rights reserved.

The role of solvent on the doping of polyaniline with Fe(III) ions

The products formed from the reaction of emeraldine base polyaniline (EB-PANI) with Fe(III) ions in N-methyl-pyrrolidone (NMP), dimethylacetamide (DMA), dimethylformamide (DMF) and m-cresol media have been investigated using UV-VIS-NIR and resonance Raman (lambda(0) = 632.8 and 1064 nm) spectroscopies. Through these results it was verified that the different PANI forms in solution can be formed by the suitable choice of the solvent. The behavior of Fe(III)/EB-PANI in different solvents was rationalized in terms of the interactions among Fe(III) ions, EB-PANI and solvent. In basic NMP, DMA and DMF media, the reaction of Fe(III) with EB-PANI yields EB-PANI doping giving ES-PANI and/or the EB-PANI oxidation to PB-PANI. The formation of ES-PANI is favored in DMF while PB-PANI is formed in a greater extension in NMP and DMA. In acidic m-cresol, only ES-PANI is produced in Fe(III)/EB-PANI solutions indicating the important role played by the solvent in the nature of the product. (C) 2010 Elsevier B.V. All rights reserved.

The role of oxygen in the interaction of emeraldine base polyaniline with Cu(II) or Fe(III) ions in NMP solution

The influence of molecular oxygen in the interactions of emeraldine base form of polyaniline (EB-PANI) with Fe(III) or Cu(II) ions in 1-methyl-2-pyrrolidinone (NMP) solutions has been investigated by UV-vis-NIR, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies. Through the set of spectroscopic results it was possible to rationalize the role Of O(2) and to construct a scheme of preferential routes occurring in the interaction of EB-PANI with Fe(III) or Cu(II). Solutions of 4.0 mmol L(-1) EB-PANI with 0.8, 2.0 and 20 mmol L(-1) Fe(III) or Cu(II) ions in NMP were investigated and the main observed reactions were EB-PANI oxidation to pernigraniline (PB-PANI) and EB-PANI doping process by pseudo-protonation, or by a two-step redox process. In the presence Of O(2), PB-PANI is observed in all Fe(III)/EB solutions and EB-PANI doping only occurs in solutions with high Fe(III) concentrations through pseudo-protonation. On the other hand, emeraldine salt (ES-PANI) is formed in all Fe(III)/EB solutions under N(2) atmosphere and, in this case, doping occurs both by the pseudo-protonation and two-step redox mechanisms. In all Cu(II)/EB solutions PB-PANI is formed both in the presence and absence of O(2), and only for solutions with high Cu(II) concentrations doping process occurs in a very low degree. The most important result from EPR spectra was providing evidence for redox steps. The determined Cu(II) signal areas under oxygen are higher than under N(2) and, further. the initial metal proportions (1:2:20) are maintained in these spectra, indicating that Cu(I) formed are re-oxidized by O(2) and. so, Cu(II) ions are being recycled. Consistently, for the solutions prepared under nitrogen, the corresponding areas and proportions in the spectra are much lower, confirming that a partial reduction of Cu(II) ions actually occurs. (C) 2009 Elsevier B.V. All rights reserved.

A study on X-ray irradiation of composite polyaniline LB films

Composite Langmuir-Blodgett (LB) films from polyaniline and cadmium stearate have been irradiated with ionizing X-rays for various exposure times. In the initial stages of X-ray irradiation the absorption peak at 580 nm of an as-deposited film was seen to decrease with a concomitant increase in the absorption in the long wavelength region (700-1100 nm). Upon prolonging the irradiation, the absorption maximum shifted to 800 nm with the LB film color changing to green, characteristic of acid doped polyaniline. The changes in the Fourier transform infrared (FTIR) spectra upon irradiation are also similar to those observed upon acid doping of polyaniline. When compared with acid doping, two major differences were observed for the LB films exposed to X-rays. First, the packing order of the cadmium stearate domains in the composite LB films - as observed by X-ray diffraction - is not affected by the X-ray irradiation. In addition, no significant increase in the DC conductivity was noted after the X-ray exposure whereas similar LB films have their conductivity increased by an order of magnitude upon acid doping. These differences may be explained by considering that the inter-domain contribution to the conductivity is increased by the acid doping because the insulating cadmium stearate domains are destroyed, which does not occur with the X-ray irradiation. (C) 1998 Elsevier B.V. S.A. All rights reserved.

Protonenleitung in imidazolhaltigen Materialien als Modellsysteme für wasserfreie Brennstoffzellenmembranen

Es wird ein neues Konzept für ein protonenleitendes Polymer vorgestellt, das ohne eine zweite, flüssige Phase auskommt. Es beruht darauf, basische Gruppen (Imidazol) über flexible Spacer kovalent an ein Polymerrückgrat zu binden und durch Dotierung mit einer geringen Menge Säure Ladungsträger (Protonen) in dieses System einzubringen.Um die für die Leitfähigkeit und ihren Mechanismus verantwortlichen Größen zu identifizieren, wurde ein Satz von niedermolekularen Modellverbindungen definierter Struktur und hoher Reinheit synthetisiert und im reinen Zustand sowie nach Dotierung mit geringen Mengen Säure umfassend charakterisiert. Untersucht wurden die thermischen Eigenschaften, die Leitfähigkeit, die Diffusion der jeweiligen Modellverbindung sowie ggf. der zugesetzten Säure, das Protonierungsgleichgewicht und die dielektrischen Eigenschaften. Insbesondere wurden durch den Vergleich von Leitfähigkeits- und Diffusionsdaten unter Anwendung der Nernst-Einstein-Beziehung Rückschlüsse auf den Leitmechanismus gezogen.Es wurden Leitfähigkeiten von bis zu 6.5E-3 S/cm bei 120°C erreicht. Der Anteil der Strukturdiffusion (vergleichbar mit dem Grotthus-Mechanismus in Wasser) an der protonischen Leitfähigkeit betrug bis zu über 90%. Als entscheidende Faktoren für die Leitfähigkeit wurden die Glastemperatur und, mit geringerer Priorität, der Imidazolgehalt des Materials identifiziert. Die Temperaturabhängigkeit aller untersuchten Transportgrößen ließ sich durch die Vogel-Tamman-Fulcher-Gleichung exzellent beschreiben.Die vorgestellten Daten bilden die Grundlage für den Entwurf eines entsprechenden Polymers.

Wasserfreie Protonenleiter für Brennstoffzellen auf der Basis von Imidazol und Benzimidazol

Mit Hilfe von Brennstoffzellen wird eine effiziente Energieumwandlung von chemischer in elektrische Energie möglich. Die kommerziellen PEM-Brennstoffzellen benutzen Membra-nen, die zum Erreichen hoher Leitfähigkeiten eine wässrige Phase erfordern, in der der Proto-nentransport stattfindet. Somit wird die Betriebstemperatur durch den Siedepunkt des Wassers limitiert. Die verwendeten Pt-Katalysatoren zeigen bei niedrigen Temperaturen eine höhere Empfindlichkeit gegenüber CO, dass im Reformierungsprozess bei der Erzeugung von Was-serstoff entsteht. Austausch der wässrigen Phase gegen Heterozyklen, die ein zu Wasser ver-gleichbares Wasserstoffbrückennetzwerk aufbauen, in dem der Protonentransport stattfinden kann, ermöglicht eine höhere Betriebstemperatur. Durch das im Laufe des Brennstoffzellen-betriebs gebildete Wasser, können die Heterozyklen verdünnt bzw. komplett aus der Memb-ran ausgewaschen werden. Daher ist es erforderlich, die Ladungsträger an ein Polymerrück-grat zu binden, so dass sie eine hohe Beweglichkeit und Konzentration, die denen in der flüs-sigen Phase einer konventionellen Membran entsprechen, aufweisen. Diese Arbeit beschreibt die Synthese und Charakterisierung von Protonenleitern, die ohne eine flüssige Phase auskommen, da sie bereits protonische Leitfähigkeit als intrinsische Ei-genschaft zeigen. Es wurden verschiedene imidazol- bzw. benzimidazolhaltige Dimere und Polythiophene, in denen Benzimidazol in der Seitenkette über verschieden flexible Spacer mit dem Polymerrückgrat verbunden ist, synthetisiert. Die Materialien wurden in undotierten Zu-stand und nach Dotierung mit geringen Mengen Phosphorsäure umfassend charakterisiert und auf thermisches Verhalten, Stabilität und Leitfähigkeit untersucht. Die benzimidazolhaltigen Dimere weisen mit 250 °C die höchsten Zersetzungstemperaturen auf. Mit zunehmender Temperatur kann in allen Fällen eine Erhöhung der Leitfähigkeit beobachtet werden, die sich in der Arrhenius-Auftragung durch eine Gerade anpassen lässt, somit kann der Protonentrans-port durch einen Protonen-hüpfmechanismus beschrieben werden. Die höchste beobachtete Leitfähigkeit liegt im Bereich von 10-6 S/cm bei 160 °C. Durch Zusatz von Phosphorsäure kann die Leitfähigkeit z.T. um einige Größenordnungen gesteigert werden. Eine Ausnahme bilden die Polythiophene, die sowohl protonische als auch elektronische Leitfähigkeit besit-zen. Hier führt die Säure zu einer Lokalisierung der Ladungsträger, so dass die elektronische Leitfähigkeit eingeschränkt wird.

New proton conducting membranes for fuel cell applications

In order to synthesize proton-conducting materials which retain acids in the membrane during fuel cell operating conditions, the synthesis of poly(vinylphosphonic acid) grafted polybenzimidazole (PVPA grafted PBI) and the fabrication of multilayer membranes are mainly focussed in this dissertation. Synthesis of PVPA grafted PBI membrane can be done according to "grafting through" method. In "grafting through" method (or macromonomer method), monomer (e.g., vinylphosphonic acid) is radically copolymerized with olefin group attached macromonomer (e.g., allyl grafted PBI and vinylbenzyl grafted PBI). This approach is inherently limited to synthesize graft-copolymer with well-defined architectural and structural parameters. The incorporation of poly(vinylphosphonic acid) into PBI lead to improvements in proton conductivity up to 10-2 S/cm. Regarding multilayer membranes, the proton conducting layer-by-layer (LBL) assembly of polymers by various strong acids such as poly(vinylphosphonic acid), poly(vinylsulfonic acid) and poly(styrenesulfonic acid) paired with basic polymers such as poly(4-vinylimidazole) and poly(benzimidazole), which are appropriate for ‘Proton Exchange Membranes for Fuel Cell’ applications have been described. Proton conductivity increases with increasing smoothness of the film and the maximum measured conductivity was 10-4 S/cm at 25°C. Recently, anhydrous proton-conducting membranes with flexible structural backbones, which show proton-conducting properties comparable to Nafion have been focus of current research. The flexible backbone of polymer chains allow for a high segmental mobility and thus, a sufficiently low glass transition temperature (Tg), which is an essential factor to reach highly conductive systems. Among the polymers with a flexible chain backbone, poly(vinylphosphonic acid), poly(vinylbenzylphosphonic acid), poly(2-vinylbenzimidazole), poly(4-styrenesulfonic acid), poly(4-vinylimidazole), poly(4-vinylimidazole-co-vinylphosphonic acid) and poly(4-vinylimidazole-co-4-styrenesulfonic acid) are interesting materials for fuel cell applications. Synthesis of polybenzimidazole with anthracene structural unit was carried out in order to avoid modification reaction in the imidazole ring, because anthracene would encourage the modification reaction with an olefin by Diels-Alder reaction.

Structure, organization and dynamics of functional supramolecular materials studied by solid-state NMR

Functional materials have great importance due to their many important applications. The characterization of supramolecular architectures which are held together by non-covalent interactions is of most importance to understand their properties. Solid-state NMR methods have recently been proven to be able to unravel such structure-property relations with the help of fast magic-angle spinning and advanced pulse sequences. The aim of the current work is to understand the structure and dynamics of functional supramolecular materials which are potentially important for fuel-cell (proton conducting membrane materials) and solar-cell or plastic-electronic applications (photo-reactive aromatic materials). In particular, hydrogen-bonding networks, local proton mobility, molecular packing arrangements, and local dynamics will be studied by the use of advanced solid-state NMR methods. The first class of materials studied in this work is proton conducting polymers which also form hydrogen-bonding network. Different materials, which are prepared for high 1H conduction by different approaches are studied: PAA-P4VP, PVPA-ABPBI, Tz5Si, and Triazole-functional systems. The materials are examples of the following major groups; - Homopolymers with specific functional groups (Triazole functional polysiloxanes). - Acid-base polymer blends approach (PAA-P4VP, PVPA-ABPBI). - Acid-base copolymer approach (Triazole-PVPA). - Acid doped polymers (Triazole functional polymer doped with H3PO4). Perylenebisimide (PBI) derivatives, a second type of important functional supramolecular materials with potent applications in plastic electronics, were also investigated by means of solid-state NMR. The preparation of conducting nanoscopic fibers based on the self-assembling functional units is an appealing aim as they may be incorporated in molecular electronic devices. In this category, perylene derivatives have attracted great attention due to their high charge carrier mobility. A detailed knowledge about their supramolecular structure and molecular dynamics is crucial for the understanding of their electronic properties. The aim is to understand the structure, dynamics and packing arrangements which lead to high electron conductivity in PBI derivatives.

Pt-Doped and Pt-Supported La1-xSrxCoO3: Comparative Activity of Pt4+ and Pt-0 Toward the CO Poisoning Effect in Formic Acid and Methanol Electro-oxidation

Pt-supported La1-xSrxCoO3 and Pt-doped La1-xSrxCoO3 are synthesized using chemical reduction and solution combustion method, respectively. Chemical reduction is carried out using formaldehyde as a reducing agent giving Pt-supported La1-xSrxCoO3. Solution combustion method is used to prepare Pt-doped La1-xSrxCoO3. Detailed characterization using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) surface area measurement, and transmission electron microscopy (TEM) is carried out to distinguish the Pt-supported and Pt-doped compounds in terms of their morphology and Pt oxidations states. TEM results indeed show the differences in their morphology. Further, electrochemical measurements are performed in neutral medium to differentiate their electrochemical activity. Cyclic voltammetry (CV) shows noticeable differences between Pt-supported La1-xSrxCoO3 and Pt-doped La1-xSrxCoO3. Importantly, our results show that Pt4+ in doped compound has poor to zero electrocatalytic activity toward formic acid and methanol electro-oxidation in comparison to Pt-0 in supported compound. This study shows that metallic Pt in zero oxidation state is a superior catalyst to Pt in +4 oxidation state.