Polymerization Of EDOT Research Articles

In situ polymerization of EDOT onto sulfonated onion-like carbon for efficient pseudocapacitor electrodes

A facile and scalable approach to combine the mechanical and capacitive advantages of onion-like carbon (OLC) with the pseudocapacitance of PEDOT in a templated architecture without dead volume and binder was developed.

Polymerization of EDOT functionalized star-shaped pentaerythritol and study of the structure and conducting properties of polymers

Pentaerythritol-based conducting polymers envisioned as an ultimate solution to obtain highly nanostructured conducting polymers with textural and conducting properties controllable by the monomer concentration in the polymerization bath.

Ag Nps@PEDOT Nanocomposite Electrosynthesis at a Polarised Liquid|Liquid Interface

One of Material Science's main challenges is constantly searching for new versatile materials. In this sense, nanocomposites have emerged as an alternative to new substrates due to their unique properties. These hybrid systems are made up of organic polymers with inorganic components. This ideal "tandem" is made up of organic polymers (for example, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy) and polyaniline (PANI)) with conductive characteristics because of their highly p-conjugated polymeric chains, unique properties, reversible doping/de-doping processes, and controllable chemical/electrochemical properties. Inorganic compounds, such as metallic nanoparticles (NPs), in the organic matrix provide a high surface area and conductivity, acting as protuberances and highly conductive fillers to form a class of material with multidisciplinary applications [1].There are several methods to generate organic polymers; the electrochemical process is one of the most used due to its versatility and simplicity. This method implies the electrodeposition of the organic polymer on an electrode surface, eliminating the possibility of obtaining a polymeric material separated from the electrode surface and limiting the areas of applicability (polymer firmly attached to the electrode surface). In this sense, the use of a polarised immiscible liquid|liquid (L|L) interfaces is demonstrated as a novel approach for the electrosynthesis of surfactant-free organic thin films, allowing complete control over the thin film morphology [2].In this work, we present the electrosynthesis of silver nanoparticles@PEDOT nanocomposites based on EDOT polymerization (PEDOT) and the formation of silver nanoparticles by electrochemical polymerisation at a polarised L|L interface. In thermodynamic terms, the oxidant potential of silver ions is insufficient to oxidise 3,4-ethylenedioxythiophene and generate PEDOT. However, under specific conditions (detailed in this presentation), silver ions are reduced while EDOT monomers are oxidised to PEDOT. A deep knowledge of biphasic electropolymerisation coupled with silver nanoparticle formation will help advance the search for new materials for a broad spectrum of applications (antibacterial, electrocatalysis, SERS substrates, biocompatibility substrates, etc.).

PEDOT-Coated PLA Fibers Electrospun from Solutions Incorporating Fe(III)Tosylate in Different Solvents by Vapor-Phase Polymerization for Neural Regeneration.

Therapeutic solutions for injuries in the peripheral nervous system are limited and not existing in the case of the central nervous system. The electrical stimulation of cells through a cell-supporting conductive scaffold may contribute to new therapeutic solutions for nerve regeneration. In this work, biocompatible Polylactic acid (PLA) fibrous scaffolds incorporating Fe(III)Tosylate (FeTos) were produced by electrospinning a mixture of PLA/FeTos solutions towards a rotating cylinder, inducing fiber alignment. Fibers were coated with the conductive polymer Poly(3,4 ethylenedioxythiophene) (PEDOT) formed by vapor-phase polymerization of EDOT at 70 °C for 2 h. Different solvents (ETH, DMF and THF) were used as FeTos solvents to investigate the impact on the scaffold's conductivity. Scaffold conductivity was estimated to be as high as 1.50 × 10-1 S/cm when FeTos was dissolved in DMF. In vitro tests were performed to evaluate possible scaffold cytotoxicity, following ISO 10993-5, revealing no cytotoxic effects. Differentiation and growth of cells from the neural cell line SH-SY5Y seeded on the scaffolds were also assessed, with neuritic extensions observed in cells differentiated in neurons with retinoic acid. These extensions tended to follow the preferential alignment of the scaffold fibers.

Multi-Layer TiO2−x-PEDOT-Decorated Industrial Fe2O3 Composites as Anode Materials for Cycle-Performance-Enhanced Lithium-Ion Batteries

An industrial submicron-sized Fe2O3 with no special shape was decorated by a multi-layer coating of oxygen-deficient TiO2−x and conducting polymer PEDOT (poly 3,4-ethylenedioxythiophene). A facile sol–gel method followed by an EDOT polymerization process was adopted to synthesize the hierarchical coating composite. The microstructure and phase composition were characterized using an X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). In particular, the existence state of PEDOT was determined using Fourier transform infrared (FT-IR) and a thermogravimetric (TG) analysis. The characterization results indicated the dual phase was well-coated on the Fe2O3 and its thickness was nano scale. Electrochemical characterization indicated that the multi-layer coating was helpful for significantly enhancing the cycle stability of the Fe2O3, and its electrochemical performance was even better than that of the single-layer coating samples. The synergistic effects of the ceramic phase and conducting polymer were demonstrated to be useful for improving electrochemical properties. The obtained FTP-24 sample exhibited a specific discharge capacity of 588.9 mAh/g after 360 cycles at a current density of 100 mA/g, which effectively improved the intrinsic cycling performance of the Fe2O3, with a corresponding discharge capacity of 50 mAh/g after 30 cycles.

Combining Step-Growth and Chain-Growth Polymerizations in One Pot: Light-Induced Fabrication of Conductive Nanoporous PEDOT-PCL Scaffold.

A novel method based on light-induced fabrication of a poly (3,4-ethylenedioxythiophene)-polycaprolactone (PEDOT-PCL) scaffold using phenacyl bromide (PAB) as a single-component photoinitiator is presented. HBr released from the step-growth polymerization of EDOT is utilized asan in situcatalyst for the chain-growth polymerization of ε-caprolactone. Detailed investigations disclose the formation of a self-assembled nanoporous electroconductive scaffold (1.2 mScm-1 ). Fluorescence emission spectra of the fabricated scaffold exhibit a mixed solvatochromic behavior, indicating specific interactions between the self-assembled scaffold and solvents with varying polarities, as evidenced by transmission electron microscopy (TEM). Moreover, the same light-induced technique can also be applied for bulk photopolymerization showcasing the versatility and wide-ranging scope of the originated method. In brief, this study introduces a novel approach for light-induced polymerization reactions that is merging step-growth and chain-growth mechanisms. This innovative approach is promising to facilitatein situpolymerization of monomers possessing diverse functionalities.

Novel Insight into the Photophysical Properties and 2D Supramolecular Organization of Poly(3,4-ethylenedioxythiophene)/Permodified Cyclodextrins Polyrotaxanes at the Air-Water Interface.

Two poly(3,4-ethylenedioxythiophene) polyrotaxanes (PEDOT∙TMe-βCD and PEDOT∙TMe-γCD) end-capped by pyrene (Py) were synthesized by oxidative polymerization of EDOT encapsulated into TMe-βCD or TMe-γCD cavities with iron (III) chloride (FeCl3) in water and chemically characterized. The effect of TMe-βCD or TMe-γCD encapsulation of PEDOT backbones on the molecular weight, thermal stability, and solubility were investigated in depth. UV-vis absorption, fluorescence (FL), phosphorescence (PH), quantum efficiencies, and lifetimes in water and acetonitrile were also explored, together with their surface morphology and electrical properties. Furthermore, dynamic light scattering was used to study the hydrodynamic diameter (DH) and z-potential (ZP-ζ) of the water soluble fractions of PEDOT∙TMe-βCD and PEDOT∙TMe-γCD. PEDOT∙TMe-βCD and PEDOT∙TMe-γCD exhibited a sharp monodisperse peak with a DH of 55 ± 15 nm and 122 ± 32 nm, respectively. The ZP-ζ value decreased from -31.23 mV for PEDOT∙TMe-βCD to -20.38 mV for PEDOT∙TMe-γCD, indicating that a negatively charged layer covers their surfaces. Surface pressure-area isotherms and Brewster angle microscopy (BAM) studies revealed the capability of the investigated compounds to organize into sizeable and homogeneous 2D supramolecular assemblies at the air-water interface. The control of the 2D monolayer organization through the thermodynamic parameters of PEDOT∙TMe-βCD and PEDOT∙TMe-γCD suggests potential for a wide range of optoelectronic applications.

Simultaneous Polymerization Acceleration and Mechanical Enhancement for Printing a Biomimetic PEDOT Adhesive by Coordinative and Orthogonal Ruthenium Photochemistry

Conductive hydrogels are promising material candidates in fields ranging from flexible sensors and electronic skin applications to personalized medical monitoring. However, developing intrinsically conductive polymer hydrogels (ICPHs) with high mechanical properties and excellent printability is still challenging. Here, we introduce a simultaneous polymerization acceleration and mechanical enhancement (SPAME) strategy to construct PEDOT-based ICPHs via the rational design of coordinative and orthogonal ruthenium photochemistry (CORP). This orthogonal photochemistry triggers the oxidative polymerization of EDOT and the coupling of phenols within seconds under blue light irradiation. Benefiting from the bifunctional EDTA-Fe design, the photoreleased Fe(III) accelerated the EDOT polymerization and shortened the preparation time of ICPHs to a few seconds. At the same time, the addition of EDTA-Fe enhanced their mechanical properties, and both the critical strains and maximum stresses of the hydrogel doubled. Furthermore, the introduction of phenol residues in PAA-Ph significantly shortened the gelation time from several minutes to about 7 s. Thus, this fast and controllable CORP chemistry is compatible with standard printing techniques for engineering hydrogels for complex multifunctional structures for multifunctional bioelectronics and devices.

Green and efficient electrosynthesis of poly-3,4-ethylenedioxythiophene in aqueous micellar solution of zwitterionic surfactant

In this work, a biocompatible and biodegradable zwitterionic surfactant SB3-14 (n-tetradecyl-N, N-dimethyl-3-ammonio-1-propanesulfonate) was chosen to replace nonionic surfactant polyoxyethylene-10-laurylether (C12E10) to solubilize the poorly water-soluble monomer 3,4-ethylenedioxythiophene (EDOT), and in the micellar solution of SB3-14, the anodic polymerization of EDOT was studied to demonstrate the advantage of the zwitterionic surfactant over the nonionic surfactant. Compared with C12E10, SB3-14 is neither adsorbed on the glassy carbon electrode (GCE) over −0.2～1.0 V vs SCE, nor oxidized at the high oxidative polymerization potential for EDOT. These unique properties are favorable not only for the enhancement of the electropolymerization rate, but also for the improvement of the current efficiency. A comparative study on the electropolymerization modes, i.e., the constant potential mode and the pulsed potential mode, indicates that at high oxidative polymerization potential, the EDOT electropolymerization reaction is limited by the diffusion mass transfer of the electroactive monomer, and the growth rate of the polymer PEDOT can be significantly increased by prolonging the duration time of the pulse lower limit potential. At low oxidative polymerization potential, however, the EDOT polymerization reaction is basically controlled by the heterogeneous charge transfer process, and the electropolymerization modes have little effect on the growth rate of the PEDOT film. The XPS data of the PEDOT films demonstrate that SB3-14 is not doped (encapsulated) into the PEDOT film, and ClO4− is the only doping species. The doping level of the PEDOT film is determined by the oxidative polymerization potential and the electropolymerization mode. At high oxidative polymerization potential, the pulsed potential mode results in a PEDOT film with higher doping level than the constant potential mode does due to the periodic relaxation of the monomer concentration gradient as well as the full doping of the polymer in the duration time of the pulse lower limit potential. The above studies demonstrate that this new strategy is helpful for the green and efficient electrosynthesis of high quality PEDOT.

Hydrophilic polyelectrolyte microspheres as a template for poly(3,4-ethylenedioxythiophene) synthesis.

Conducting polymer polyelectrolyte microspheres are typically composed of a cationic conducting polymer and an anionic polymer. The polymer chains inside these microspheres are physically or chemically cross-linked, creating a network that enables high water retention. Poly(3,4-ethylenedioxythiophene) (PEDOT) being an electrically conductive polymer exhibits a high conductivity and has great biotechnological applications. The unique combination of properties of PEDOT containing polyelectrolyte microspheres makes them widely investigated materials for electroresponsive cells, tissue engineering, and bio-sensors. The demand to produce PEDOT with varied properties depending the specific application requires the understanding of the basic principles of template formation. In the present work, we studied the inverse suspension polymerization of p-styrenesulfonic acid in the presence of a cross-linking agent as a synthetic way for the formation of porous polyelectrolyte microspheres. We traced how the nature of the emulsifier affected both the structure of the surface layer of the microspheres and the degree of their cross-linking. The porous structure of polyelectrolyte microspheres obtained is found to promote the polymerization of EDOT in their presence throughout the entire microsphere volume. The structural characteristics of the polyelectrolyte/PEDOT complexes in relation to their electrochemical properties have been studied.

Oxygen-vacancy V2O5 ultrathin nanosheets adorned with PEDOT films as anodes for high-energy-density asymmetric supercapacitors

Oxygen-vacancy PEDOT/V2O5 nanosheets are obtained by the oxidative polymerization of EDOT on V2O5 without other oxidants. The energy density of supercapacitors composed of PEDOT/V2O5 and activated carbon reaches 65 W h kg−1.

Visible light enhanced photosynthesis of C-C bonds using PdO/Pd@PEDOT nanocomposite

Facile utilization of abundant and freely available solar energy in the production of fine chemicals is currently recognized as an effective strategy for sustainable chemical production. We are hereby reporting one of the best visible light active photocatalysts for C-C bond formation. The photocatalyst is a heterojunction nanocomposite of PdO/Pd with poly(3,4-ethylenedioxythiophene) (PdO/Pd@PEDOT HNC). It was synthesized via one pot chemical oxidative polymerization of EDOT with K2PdCl4. Uniform spherical morphology of the nanocomposite was achieved using a solvent assisted, and template free approach. PdO/Pd@PEDOT HNC consisted of very small Pd nanoparticles with dual oxidation states [here, Pd (II) and Pd (0)] embedded in the PEDOT matrix. It showed excellent electron-hole pair separation capabilities under visible light due to the formation of a straddling type of heterojunction between PdO and semiconducting PEDOT. PdO/Pd nanoparticles forms strong chemical interaction with PEDOT via Pd-O and Pd-S bonds in the HNC. These interactions make it a highly stable photocatalyst which can be recycled up to seven times without any significant loss of activities. Further, a novel route for the synthesis of uniform Pd4S nanostructures using a template free strategy could also be achieved.

Synthesize and characterization of sustainable natural fibers/ conductive polymer composites

This work aims to obtain reinforced composites of natural fibers that obtained from their agricultural wastes of and conductive polymers to develop an innovation and alternative materials. By the use of natural fibers contributes to the recycle of agricultural wastes, sustainability and further the resulting composite becomes alternative to the metals. Here, flexible conductive composites were obtained from artichoke(A), banana(B) and luffa(L) stem waste fibers(F) by the in-situ polymerization of 3,4-ethylene dioxythiophene (EDOT), pyrrole, and carbazole in the presence of cerium ammonium nitrate, iron nitrate, and iron chloride. Fibers were coated with the conductive polymers mentioned above by the in-situ chemical(C) polymerization and optimum coating conditions were investigated. Effect of EDOT concentration, oxidant concentration was performed to determine the optimum conditions for AF/PEDOT(C). FT-IR, SEM, thermal analysis supported the formation of composite and from the mechanical measurements, modulus of AF/PEDOT(C) was obtained. The highest conductivity of 12.8 S/cm was obtained from AF/PEDOT(C) composite using FeCl3 as an oxidant. Further polymerization of EDOT by electrochemical(E) method was continued on the AF/PEDOT(C) and the electroactivity of resulting electrochemical composite, AF/PEDOT(C)/PEDOT(E) was characterized accordingly. Detailed characterization showed that to use of this composite as a capacitor, one should use 0.03 M EDOT and 0.9 M FeCl3 for chemical polymerization and then continued by electropolymerization by applying 10 cycles in 0.03 M EDOT. All results showed that AF waste could be converted to the valuable AF/PEDOT(C)/PEDOT(E) conductive composites which is potentially suitable material for several electronic applications as charge storage, biosensor, electronic devices.

The influence of poly(3,4‐ethylenedioxythiophene) modification on the transport properties and fuel cell performance of Nafion‐117 membranes

AbstractNafion‐117/PEDOT composite membranes were synthesized by in situ chemical polymerization of 3,4‐ethylenedioxythiophene (EDOT) using ammonium persulfate as an oxidant. The polymerization of EDOT in Nafion membranes for various EDOT/oxidant treatment sequences was studied for the first time. PEDOT introduction leads to a slight decrease in both the ion‐exchange capacity and water uptake of the composite membranes, as well as to an increase in cationic transport. Membranes initially treated with an oxidant exhibit better conductivity and lower hydrogen permeability. The effect of both modification of Nafion‐117 membranes by PEDOT and hot‐pressing of hydrogen‐oxygen membrane‐electrode assemblies (MEAs) on the performance of proton‐exchange membrane fuel cells was studied. The maximum power density of the fabricated MEAs increases 1.5‐fold: from 510 (for a pristine Nafion‐117 membrane) to 810 mW cm−2 (for a membrane modified by PEDOT). The current density at a voltage of 0.4 V reaches 1248 and 2246 mA cm−2, respectively.

Cathode Materials Based on Lithium Iron Phosphate/PEDOT Composites for Lithium-Ion Batteries

Composites based on LiFePO4/C and poly(3,4-ethylenedioxythiophene) (LiFePO4/C/PEDOT) have been prepared via in situ oxidative EDOT polymerization or mechanical mixing of LiFePO4/C with presynthesized PEDOT particles, including those prepared in the presence of different surfactants (Triton X-100 and cetyltrimethylammonium bromide). The resultant materials have been characterized by X-ray diffraction, scanning electron microscopy, CNHS analysis, and IR spectroscopy. At high current densities, the best electrochemical performance has been demonstrated by the composite prepared by mechanical mixing of LiFePO4/C with a PEDOT suspension in acetonitrile (70 mAh/g at a current density of 1600 mA/g). Further increase in the discharge capacity of the LiFePO4/C/PEDOT composites at high current densities has been ensured by precoating LiFePO4/C particles with the Triton X-100 surfactant (81 mAh/g at 1600 mA/g).

Direct laser writing of nanoscale undoped conductive polymer

The fabrication of poly 3,4-ethylene dioxythiophene (PEDOT) devices generally requires a separated strategy for EDOT polymerization and PEDOT coating, thus increasing th difficulty of their integration. With the goal of insolubility of PEDOT in a common solution, material modifications including grafting vinyl moiety groups on the side chain of the PEDOT can increase its solubility, but also markedly reduce the conductivity. Here, we report direct laser writing of pure EDOT monomer into PEDOT with a feature size of 140 nm. The PEDOT nanowire possesses the high conductivity of 1.28 × 105 S m−1 and can be patterned on solid and flexible substrates with various structures, thus paving the way towards organic highly conductive device fabrication and integration.

Poly (3, 4-ethylene dioxythiophene) Supported Palladium Catalyst prepared by Galvanic Replacement Reaction for Methanol Tolerant Oxygen Reduction

Herein, we propose a facile electrochemical approach for the synthesis of Pd loaded poly 3, 4-ethylenedioxythiophene (PEDOT) electrodeposited on glassy carbon electrode (GCE) resulting in high surface area. The catalyst preparation is initiated with EDOT polymerization on GCE surface by electrochemical potential cycling method, followed by the electrodeposition of Cu from a 2 mM solution of CuSO4 in 0.1 M NaClO4 at a constant potential of +0.34 V vs. SHE in the form of Cu nanocubes on the PEDOT surface. Pd-PEDOT catalyst was then prepared by the partial substitution of copper by galvanic displacement with various concentrations of PdCl2. The prepared Pd/PEDOT electrocatalyst is found to be methanol resistant indicating its usefulness as fuel cell cathode. The prepared catalyst supports two electron transfer of oxygen reduction reaction in 0.5 M H2SO4. The effects of Pd and Cu contents and the quantity of PEDOT, mass and specific activities were studied. At a relatively low Pd loading of 0.57 ng/cm2, the Pd/PEDOT should be a cost-effective alternative cathode catalyst for direct methanol fuel cells, DMFCs. This work explains the usefulness of PEDOT as good catalyst supporting material which is prepared by an eco-friendly electrochemical route.

Producing and investigation of PEDOT films as electrodes of ionic electroactive actuators

Experimental samples of ionic electroactive actuators with poly(3,4-ethylenedioxythiophene) electrodes (PEDOT) have been developed and produced. Measurements of amplitudes of a displacement, frequency and power characteristics of produced actuators were carried out. The influence of the membrane solvent, as well as the influence of the EDOT polymerization time on the sample structure and the output characteristics of actuators, was determined.

Printing PEDOT from EDOT via plasma-assisted inkjet printing

We demonstrate the simultaneous polymerization of 3,4-ethylenedioxythiophene (EDOT) monomer stock solution ink and printing of the resulting poly(3,4-ethylenedioxythiophene) (PEDOT) via plasma-assisted inkjet printing. The plasma-induced polymerization of EDOT is confirmed via Raman and Fourier-transform infrared (FT-IR) spectroscopies of the printed line. Furthermore, we also achieve plasma-induced polymerization of PEDOT with poly(styrenesulfonate) (PSS) for the synthesis of an electrically conductive film from EDOT. Consequently, we fabricate a PEDOT/PSS film with conductivity of the order of 10−2 Scm−1 on a borosilicate glass substrate. Our approach achieves (i) direct patterning with PEDOT polymerization and (ii) doping with PEDOT polymerization as separate processes, and our results suggest that on-site printing of conductive PEDOT/PSS with polymerization is possible through the use of an inkjet system with resistance to even the strong acidity of PSS.

A highly stretchable large strain sensor based on PEDOT–thermoplastic polyurethane hybrid prepared via in situ vapor phase polymerization

Strain sensors based on percolated networks of poly(3,4-ethylenedioxythiophene) (PEDOT) in thermoplastic polyurethane (TPU) matrix fabricated through in situ vapor phase polymerization (VPP) is reported. The hybrid made of elastomer and conductive polymer shows uniform PEDOT distribution on the surface and inner side of the TPU due to the effective penetration, diffusion, and polymerization of EDOT. Performance of sensors using two kinds of oxidants (FeCl3 or iron(III) p-toluenesulfonate(FTS)) are compared and the concentration is varied to obtain the best electromechanical properties. Amount of PEDOT increases with increasing amount of oxidant: thereby improving the electrical conductivity, while the elasticity of the hybrid decreases. The elasticity reduction phenomenon is diminished when FTS is used due to the plasticizer effect of the tosylate ion on the TPU. The performances of PEDOT–TPU hybrids prepared with FTS are excellent in the terms of stretchability (>300%), gauge factor (GF > 10 @ strain 100%), resistance variation reproducibility under various strain modes, small hysteresis, and durability (>1000 cycle). With the electromechanical performance, as well as cheap and scalable production, the PEDOT/TPU sensor holds tremendous prospects on flexible and stretchable devices for human motion monitoring, as well as present strategies on architecture of conductive soft materials.