Synthesis Of Polythiophene Research Articles

Synthesis of polythiophene with zigzag morphology on pencil graphite electrode and investigation of energy storage properties in supercapacitors

Herein, polythiophene-based supercapacitor electrode materials were successfully synthesized by the electropolymerization method. Thymol blue, bromothymol blue, and bromophenol blue were added to the polythiophene polymerization medium as dopants, and the energy storage properties of the thiophene-based electrode material were investigated. Polythiophene/bromothymol blue (PTh/BTB) gave the polythiophene an interesting zigzag morphology, which is unique in the literature (specific surface area of PTh/BTB and PTh: 32.629 m2 g−1 and 13.812 m2 g−1). The electrode performance of PTh/BTB shows a maximum specific capacitance of 443.5 F g−1 at 5 mV s−1. The symmetrical supercapacitor achieved a maximum energy density of 9.7 Wh kg−1 and a maximum power density of 5000 W kg−1. The capacitance retention value exhibited a steady state of 79.2% up to 10,000 cycles.Graphical abstract

Block sequence dependent self-assembly and optoelectronic behavior of thermo- and pH-sensitive Polythiophene-graft-[Poly(diethylene glycol methyl ether methacrylate)-block-Poly(dimethyl amino ethyl methacrylate)] copolymers

To overcome the difficulty of using multistep process we report an one pot synthesis of polythiophene (PT)-graft block copolymers with thermo-sensitive poly(diethyleneglycol methyl ether methacrylate)(PDEGMEM) and pH-sensitive poly(dimethyl amino ethyl methacrylate)(PDMAEMA) using ATRP technique. The polymers PT-g-(PDEGMEM10-b-PDMAEMA3) (P1), PT-g-(PDMAEMA10-b-PDEGMEM3) (P2) and PT-g-(PDMAEMA6-ran-PDEGMEM8) (P3) are characterized by 1H NMR and SEC techniques. HRTEM study shows that P1 and P3 exhibit micellar morphology but P2 shows vesicular morphology, all sizes increase with increasing pH and temperature. UV–vis absorption spectra show pH, temperature and sequence dependent absorbance peak, and dc-conductivity (P2 > P3 > P1) indicates semi-conducting nature. Current-Voltage (I-V) property shows pH dependent memory and OMEIC property following above order. At pH3, on irradiation with white light the photocurrent gains of P2, P3 and P1 are 7.9, 6.6 and 3.5, respectively. Thus PT-graft block copolymers exhibit tunable self-assembly, optoelectronic, transport and photocurrent properties depending on proximity and preponderance of block sequence from PT backbone and also for their pH and thermo-responsivity.

Base-Assisted Polymerizations of Elemental Sulfur and Alkynones for Temperature-Controlled Synthesis of Polythiophenes or Poly(1,4-dithiin)s.

With the increasing demand for functional polythiophenes in extensive applications such as organic solar cells, electronic skins, thermoelectric materials, and field effect transistors, efficient and economic synthetic approaches for polythiophenes are urgently required. In this work, KOH-assisted polymerizations of elemental sulfur and alkynones were developed to directly afford polythiophenes with various backbones, regioselective structures, and high molecular weights (Mns up to 20700 g/mol) in high yields (up to 97%) at 80 °C in 30 min. When the same polymerization was conducted at room temperature, stable and unique poly(1,4-dithiin)s (Mns up to 21800 g/mol) could be rapidly obtained in high yields (up to 87%) in 10 min. The temperature-controlled KOH-assisted polymerizations of sulfur and alkynones possessed high efficiency, mild conditions, and simple operation, which had provided an economic, efficient, and convenient approach for the direct conversion from elemental sulfur to functional polythiophenes and poly(1,4-dithiin)s with the in situ constructed aromatic or nonaromatic heterocycles embedded in the polymer backbones, demonstrating great synthetic simplicity, high efficiency, good selectivity, and robustness. It is anticipated to accelerate the development of semiconducting polymer materials and their applications.

One-Step Synthesis of Polythiophene as a Potential Adsorbent for Removal of As (III) and As (V) from Aqueous Solution

One-Step Synthesis of Polythiophene as a Potential Adsorbent for Removal of As (III) and As (V) from Aqueous Solution

In Situ Synthesis of Polythiophene and Silver Nanoparticles within a PMMA Matrix: A Nanocomposite Approach to Thermoelectrics

In Situ Synthesis of Polythiophene and Silver Nanoparticles within a PMMA Matrix: A Nanocomposite Approach to Thermoelectrics

Generation of Sodium‐Thiophene Species with Metal Amide‐Free Approach Toward Polythiophene Synthesis by Cross‐Coupling Polymerization

AbstractDeprotonative metalation of 2‐halo‐3‐substituted thiophene in a metal amide‐free manner takes place at the 5‐position smoothly in the presence of additive N,N,N′,N′‐tetramethylethylenediamine (TMEDA) at room temperature in a hexane solution. Following addition of nickel catalyst to the thus formed thiophene‐sodium species promotes cross‐coupling polymerization. When toluene was employed as a solvent in the polymerization reaction of 2‐chloro‐3‐hexylthiophene in the presence of 2 mol% of nickel catalyst bearing N‐heterocyclic carbene ligand, polythiophene was obtained in up to 86% yield with Mn of 23700 (Mw/Mn=1.98) suggesting that ca. 30% of the catalyst participated in the polymerization.

Synthesis of polythiophene and their application

Synthesis of polythiophene and their application

One-Shot Deprotonative Metalation/Transmetalation/Polymerization of Halothiophenes Catalyzed by Nickel Complex for Polythiophene Synthesis

AbstractEffect of divalent metals was studied in the cross-coupling polymerization of thiophenes leading to head-to-tail-type poly-3-hexyl­thiophene. Deprotonation of the C–H bond at the 5-position of 2-halo-3-hexylthiophene by LDA followed by metal exchange was carried out in one pot and following addition of nickel catalyst underwent polymerization. One-shot reaction involving deprotonation/transmetalation/ cross coupling polymerization was also examined with manganese(II) chloride and nickel(II) catalyst.

Synthesis of polythiophene containing heterocycle on the side chain: A review

AbstractThis review highlights some synthesis results of ionic and neutral conjugated polythiophenes containing heterocyclic moieties on side chain using oxidative or cross‐coupling polymerizations. Because of their increasing importance in material science, a lot of methods have recently been developed for their synthesis and modification. The review also reported out that conjugated polythiophenes exhibit special optical and electrical properties with high solubility in water making potential applications of these polymers from aqueous solutions, which can facilitate the preparation of the composites of these polymers. The art of designing side chains with various sizes, electronic properties and polarities was demonstrated to be necessary for fine‐tuning the solubility and other properties of polythiophenes, thereby enhancing their applications as advanced materials.

DC electrical conductivity and liquefied petroleum gas sensing application of polythiophene/zinc oxide nanocomposite

Despite being a versatile fuel, liquefied petroleum gas (LPG) is extremely flammable even at very low concentration of 1000 ppm. Therefore, detection of LPG below the 1000 ppm is necessary for safety point of view. Herein, we are reporting the synthesis of polythiophene (PTh) and polythiophene/zinc oxide nanocomposite (PTh/ZnO) through in-situ chemical oxidative polymerization method. The structure and morphology of as-synthesized materials were determined by various techniques such as SEM, FTIR, XRD and TEM. The stability of DC electrical conductivity of PTh and PTh/ZnO nanocomposites under an accelerated isothermal as well as cyclic ageing conditions were evaluated. Both the conductivity and stability of PTh significantly improved by incorporating a small amount of ZnO nanoparticles. We also studied LPG sensing performances of pelletized form sensors based on PTh and PTh/ZnO-3 by alternate exposure in LPG atmosphere and ambient air. The lower detection limit of PTh/ZnO-3 was found to be 600 ppm. PTh/ZnO-3 based sensor exhibited about 1.58 and 4.9 times greater sensing efficiency in terms of sensing response and reversibility as compared to the pristine PTh based sensor at 2400 ppm.

Synthesis, characterisation and ethanol sensing application of polythiophene/graphene nanocomposite

Nowadays, intrinsically conducting polymers, and nanostructured carbon materials based sensors have been fabricated extensively because of their outstanding sensitivity, reversibility, stability and selectivity at low working temperature. Herein, we are reporting nanocomposite of polythiophene (PTh) with graphene nanosheets (G) as a potential candidate for ethanol vapour sensor application with high sensitivity and complete reversibility at room temperature. The cost-effective and simple in-situ chemical oxidative polymerisation technique was employed for the synthesis of PTh and PTh/G. The structural, morphological and thermal studies of as-prepared materials were carried out by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmittance electron microscopy (TEM), Raman spectroscopy, x-ray diffraction (XRD) and thermogravimetric analysis (TGA) techniques. We evaluated the comparative DC electrical conductivity retention under the isothermal and cyclic ageing conditions for all the as-prepared samples, and thus PTh/G-3 (PTh/G nanocomposite containing 15% graphene nanosheets) was found to be most stable semiconductor among all the as-prepared materials with initial DC electrical conductivity of 0.6874 Scm−1. The results revealed that thiophene monomer successfully polymerised on the surface of graphene nanosheets as a result of an electronic as well as π-π interaction between PTh and graphene nanosheets. Hopping of charge carriers from PTh to graphene nanosheets and vice versa where the extended π-conjugated system provides rapid mobility that brings about exceptionally enhanced electrical conductivity in PTh/G nanocomposites as compared to PTh. The change in DC electrical conductivity of PTh/G-3 nanocomposite was studied on exposure to ethanol vapours followed by ambient air at room temperature. It was observed that the uniform lamination of PTh on graphene nanosheets shows the excellent sensitivity than PTh, leading to a considerably low detection limit of 400 ppm and complete reversibility within 360 s at room temperature. The very short response time and complete reversibility may be accredited to the very high surface area of PTh/G-3, high electrical conductivity, availability of proper sensing pathways and active sites. More notably, PTh/G-3 was observed to be excellent in selectivity towards ethanol than various volatile hydrocarbons tested. The sensing mechanism was presented citing the involvement of polarons of polythiophene and lone pairs of electrons of ethanol during adsorption and desorption on the surface of PTh/G-3 which is responsible for the variation in DC electrical conductivity.

Microwave assisted synthesis of polythiophene–molybdenum sulfide counter electrode in dye sensitized solar cell

This work focuses on the microwave assisted synthesis of polythiophene–molybdenum sulfide (PTh/MoS2) composite as a counter electrode (CE) in dye sensitized solar cell (DSSC). The structural characterizations of the prepared samples were examined through different techniques including FT-IR spectroscopy, FESEM, EDAX, XRD, and XPS. The cyclic voltammetry and electrochemical impedance spectroscopy results shows that the composite possesses better electro-catalytic activity with 22% lower charge transfer resistance in comparison with PTh which is in good agreement with Tafel curves results. The DSSC fabricated with PTh/MoS2 composite as CE exhibited a short circuit density (JSC) of 6.01 mA cm−2, fill factor of 0.5 and power conversion efficiency (η) of 1.36% which is 38% higher than the cell fabricated with PTh under full light illumination (100 mW cm−2 AM 1.5G). Hence the high performance PTh/MoS2 composite can be potentially used as a cost effective and efficient counter electrode for dye sensitized solar cell.

Identifying the missing link in catalyst\xa0transfer polymerization

Nickel-catalyzed catalyst transfer polycondensation (CTP) of thiophenes is an efficient strategy for the controlled synthesis of polythiophenes. However, a detailed view of its reaction mechanism has remained elusive with unresolved questions regarding the geometry and bonding of critical Ni(0) thiophene intermediates. Herein, we provide experimental and computational evidence of structurally characterized square planar η2-Ni(0)–thiophene species and their relevance to the mechanism of CTP. These results confirm the viability of C,C-η2 bound intermediates in CTP of thiophenes, providing an electronic rationale for the stability of such species, and thus that such processes can proceed as living polymerizations. We further show that C,S-κ2 species may also be relevant in nickel-catalyzed CTP of thiophenes, providing new avenues for exploitation and optimization.

Functionalization of poly(bis‐thiophene methine)s via facile C–C bulk polymerization and their application as chemosensors for acid detection

ABSTRACTUp to now, 3,4‐ethylenedioxythiophene (EDOT) or its modified analogs are indispensable units or subunits in all successful monomers for polythiophene synthesis through solid‐state polymerization (SSP). Here, a more open thiophene‐(CH(R))‐thiophene platform was developed successfully and corresponding poly(bis‐thiophene methine)s were obtained via C–C SSP or melt‐state polymerization (MSP), that is, bulk polymerization. Meanwhile, the observation of quite long effective Br–Br distance of 5.634 Å, which is more than 50% of halogen's double van der Waals radius (2rw), would help us to understand powerful capability of modulation of molecule movement and reaction under SSP. In addition, these polymers were further employed as acid sensors and they show highly sensitive response to HCl, MeSO3H, BF3‐OEt2, and HNO3. The detailed experiment reveals that P1 has the detection limit of 3.35 × 10−5 M for HCl. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1676–1683

A Rational Design of Highly Controlled Suzuki-Miyaura Catalyst-Transfer Polycondensation for Precision Synthesis of Polythiophenes and Their Block Copolymers: Marriage of Palladacycle Precatalysts with MIDA-Boronates.

Herein, we report a highly efficient Suzuki-Miyaura catalyst-transfer polycondensation (SCTP) of 3-alkylthiophenes using bench-stable but highly active Buchwald dialkylbiarylphospine Pd G3 precatalysts and N-methylimidodiacetic (MIDA)-boronate monomers. Initially, the feasibility of the catalyst-transfer process was examined by screening various dialkylbiarylphospine-Pd(0) species. After optimizing a small molecule model reaction, we identified both RuPhos and SPhos Pd G3 precatalysts as excellent catalyst systems for this purpose. On the basis of these model studies, SCTP was tested using either RuPhos or SPhos Pd G3 precatalyst, and 5-bromo-4- n-hexylthien-2-yl-pinacol-boronate. Poly(3-hexylthiophene) (P3HT) was produced with controlled molecular weight and narrow dispersity for a low degree of polymerization (DP) only, while attempts to synthesize P3HT having a higher DP with good control were unsuccessful. To improve the control, slowly hydrolyzed 5-bromo-4- n-hexylthien-2-yl-MIDA-boronate was introduced as a new monomer. As a result, P3HT and P3EHT (up to 17.6 kg/mol) were prepared with excellent control, narrow dispersity, and excellent yield (>90%). Detailed mechanistic investigation using 31P NMR and MALDI-TOF spectroscopy revealed that both fast initiation using Buchwald precatalysts and the suppression of protodeboronation due to the protected MIDA-boronate were crucial to achieve successful living polymerization of P3HT. In addition, a block copolymer of P3HT- b-P3EHT was prepared via SCTP by sequential addition of each MIDA-boronate monomer. Furthermore, the same block copolymer was synthesized by one-shot copolymerization for the first time by using fast propagating pinacol-boronate and slow propagating MIDA-boronate.

Spectroscopic, morphological, thermal and dielectrical analysis of composite of polythiophene with photoactive transition metal complex of W(IV)

The present work involves the synthesis of polythiophene–potassium octacyanotungstate(IV) dihydrate composite via in-situ oxidative chemical polymerization method using \(\hbox {FeCl}_{3}\) as an oxidant. The resulting composite has been subjected to Fourier transform infrared, X-ray diffraction (XRD) and scanning electron microscopy characterization techniques, which confirm the successful synthesis of the composite. XRD shows that the crystalline structure of \(\hbox {K}_{4}[\hbox {W(CN)}_{8}]\cdot \hbox {2H}_{2}\hbox {O}\) has been retained in the composite. Thermogravimetric analysis data confirm the higher thermal stability of the composite in comparison with pure polythiophene, thus allowing it to be used as a promising material for high-temperature application purposes. Dielectric studies reveal that the dielectric constant and ac-conductivity of the composite increased by several orders of magnitude as compared with pure polythiophene at all frequencies, thus showing that the material can be used for various applications in the fields of charge storage devices and high-frequency device applications, and can also serve as a potential candidate for solar cell applications.

Polythiophene/mesoporous SrTiO 3 nanocomposites with enhanced photocatalytic activity under visible light

Abstract In this contribution, a facile synthesis of polythiophene (PTh), using various ratios of thiophene (Th) monomers, mesoporous SrTiO 3 nanocomposites has been achieved through in-situ oxidative polymerization method. XRD patterns exhibit well-defined, sharp crystalline SrTiO 3 structure. XPS, FTIR and Raman spectra clearly revealed the formation of PTh-SrTiO 3 nanocomposites. HRTEM and FESEM images confirmed that the PTh-SrTiO 3 structure is quite similar to the undoped SrTiO 3 with fine nanoparticles size in the range of 10–20 nm. PTh-SrTiO 3 nanocomposites possessed type IV isotherm that is characteristic for mesoporous materials. BET surface area values of 0.5, 1 and 10 wt% PTh doped SrTiO 3 are 118.00 m 2 /g, 126.66 m 2 /g and 72.36 m 2 /g, respectively. The photocatalytic performance of PTh-SrTiO 3 nanocomposites for MB photodegradation was performed and compared with either pure PTh or undoped SrTiO 3 under visible light illumination. The photocatalytic efficiency of the PTh-doped SrTiO 3 nanocomposites is superior to that of either pure PTh or undoped SrTiO 3 . 1% PTh-SrTiO 3 nanocomposite exhibits the highest photocatalytic performance with more than 90% MB photodegradation. The photodegradation rate of 1% PTh-SrTiO 3 nanocomposite is greater 4.75 times than that of pure PTh or undoped SrTiO 3 . This is explained by its large surface area, synergetic effect that led to efficient separation of the photogenerated charge carriers, low band gap energy and mesoporous structure.

Synthesis of Polythiophene⁻Fullerene Hybrid Additives as Potential Compatibilizers of BHJ Active Layers.

Perfluorophenyl functionalities have been introduced as side chain substituents onto regioregular poly(3-hexyl thiophene) (rr-P3HT), under various percentages. These functional groups were then converted to azides which were used to create polymeric hybrid materials with fullerene species, either C60 or C70. The P3HT–fullerene hybrids thus formed were thereafter evaluated as potential compatibilizers of BHJ active layers comprising P3HT and fullerene based acceptors. Therefore, a systematic investigation of the optical and morphological properties of the purified polymer–fullerene hybrid materials was performed, via different complementary techniques. Additionally, P3HT:PC70BM blends containing various percentages of the herein synthesized hybrid material comprising rr-P3HT and C70 were investigated via Transmission Electron Microscopy (TEM) in an effort to understand the effect of the hybrids as additives on the morphology and nanophase separation of this typically used active layer blend for OPVs.

Electrochemical synthesis of polythiophene–polyacrylamide composite coatings used for pseudocapacitors

Polythiophene films have been electrochemically deposited onto uncoated and coated with polyacrylamide steel mesh. It has been found that the specific capacitance of the polythiophene film deposited on a sublayer of polyacrylamide was 30% higher than of the film of polythiophene deposited on the steel mesh without the underlayer.

One Step Synthesis of Polythiophenes from the Partially Purified Crude Extract of the Roots of Tagetes Erecta

<p>Polythiophene and its derivatives are valuable conjugated polymers due to their physical properties and applications in various fields. Precursors of polythiophenes were conventionally obtained from petrochemical byproducts, which are non-renewable. Thiophene and its derivatives had been found naturally in <em>Tagetes</em> species such as <em>Tagetes erecta, Tagetes tenuifolia</em>,<em> </em>etc. <em>Tagetes</em> species produce 2, 2’:5’, 2’’-terthienyl (Alpha-T), 5-(3-buten-1-ynyl)-2, 20-bithienyl (BBT), 5-(4-hydroxy-1-butynyl)-2, 20-bithienyl (BBTOH), and 5-(4-acetoxy-1-butynyl)-2, 20-bithienyl (BBTOAc), which are accumulated in different parts, specifically in the roots of the plants. These thiophene derivatives were extracted and identified by GC-MS, Uv-vis, FTIR and TLC analysis. The partially purified plant extract is polymerized through one step oxidative free radical polymerization to obtain polythiophenes. Product characterization has revealed that the selective polymerization of thiophene derivatives results in the phase-separated end product from the rest of the materials in the plant-extract.</p>