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Conductive Polymers: Materials and Applications

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Smart Materials".

Deadline for manuscript submissions: closed (31 January 2020) | Viewed by 42728

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Dr. César Quijada

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Departmento de Ingeniería Textil y Papelera, Universitat Politècnica de València, Pza Ferrándiz i Carbonell, E03801 Alcoy (Alicante), Spain
Interests: electrochemistry of conducting polymers; electrode materials for energy systems and environmental applications; electrochemical processing of textile fabrics
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Special Issue Information

Dear Colleagues,

Since the breaktrough discovery of polyacetylene, the first conducting polymer, made by Chemistry Nobel Prize laureates Heeger, MacDiarmid and Shirakawa in the 1970s, the interest in these fascinating family of materials has expanded incessantly to become a well-established area of highly dynamic, multidisciplinary research. The electron conductivity of conducting polymers (CPs) can be easily tuned by facile and reversible doping/dedoping to range from insulating to semiconducting to metallic, thus enabling control of unique optical, physical and redox properties. Jointly with low cost and the vast repertory of synthetic organic chemistry or electrochemistry available to produce lightweight and flexible tailored structures, the above properties have made these materials attractive to a broad spectrum of applications with high technological impact, many of them reaching marketplace. Some usual examples are light-emitting devices and solar cells, electrochromic devices, (bio)sensors and actuators, secondary batteries and supercapacitors, artificial muscles or electromagnetic interference (EMI) shielding and microwave absorbing materials. Additionally, new applications in biomedical science and tissue engineering, in electrochemically-enhanced solid-phase mictroextraction or as adsorbent/ion-exchange materials for environmental issues are emerging as promising growth areas.

This Special Issue is intended to cover the latest advances and developments in the synthesis, characterization, structure-properties relationship and applications of electrically conducting polymers, with particular attention to the role of nanosized shape and the properties of novel CP-inorganic hybrid composite nanostructures. Topics including, but not limiting to, synthesis, characterization and properties study of new conducting polymers from novel functionalized monomer derivatives, development of methods for controlled growth of nanostructures (interfacial, micellar, templated, molecularly imprinted or other structure-directing polymerization), novel hybrid CP composite nanoarchitectures with metal oxide nanoparticles, carbon materials or clays and applications of the above materials in the fields of optoelectronics, energy production and storage, environment, sensing, and so on, are all welcome.

It is my pleasure to invite you to contribute to this Special Issue. Original, high-quality research articles and reviews are encouraged for submission.

Assoc. Prof. Dr. César Quijada
Guest Editor

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Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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Keywords

Conducting polymers
Novel functionalized monomers
Structure-directing polymerization
Hybrid conducting-polymer-inorganic nano composites
Structure, properties and materials characterization
Functional and smart materials
Optoelectronic and solar cell devices
Energy generation and storage
(Bio)sensing and analysis
Pollution abatement

Published Papers (10 papers)

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Editorial

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4 pages, 190 KiB

Open AccessEditorial

Special Issue: Conductive Polymers: Materials and Applications

by César Quijada

Materials 2020, 13(10), 2344; https://doi.org/10.3390/ma13102344 - 20 May 2020

Cited by 18 | Viewed by 2880

Abstract

Intrinsically conductive polymers (CPs) combine the inherent mechanical properties of organic polymers with charge transport, opto-electronic and redox properties that can be easily tuned up to those typical of semiconductors and metals. The control of the morphology at the nanoscale and the design of CP-based composite materials have expanded their multifunctional character even further. These virtues have been exploited to advantage in opto-electronic devices, energy-conversion and storage systems, sensors and actuators, and more recently in applications related to biomedical and separation science or adsorbents for pollutant removal. The special issue “Conductive Polymers: Materials and Applications” was compiled by gathering contributions that cover the latest advances in the field, with special emphasis upon emerging applications. Full article

(This article belongs to the Special Issue Conductive Polymers: Materials and Applications)

Research

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10 pages, 2708 KiB

Open AccessArticle

Reactive Insertion of PEDOT-PSS in SWCNT@Silica Composites and its Electrochemical Performance

by Halima Djelad, Abdelghani Benyoucef, Emilia Morallón and Francisco Montilla

Materials 2020, 13(5), 1200; https://doi.org/10.3390/ma13051200 - 06 Mar 2020

Cited by 9 | Viewed by 2278

Abstract

Hybrid silica-modified materials were synthesized on glassy carbon (GC) electrodes by electroassisted deposition of sol-gel precursors. Single-wall carbon nanotubes (SWCNTs) were dispersed in a silica matrix (SWCNT@SiO₂) to enhance the electrochemical performance of an inorganic matrix. The electrochemical behavior of the composite electrodes was tested against the ferrocene redox probe. The SWCNT@SiO₂ presents an improvement in the electrochemical performance towards ferrocene. The heterogeneous rate constant of the SWCNT@SiO₂ can be enhanced by the insertion of poly(3,4-Ethylendioxythiophene)-poly(sodium 4-styrenesulfonate) PEDOT-PSS within the silica matrix, and this composite was synthesized successfully by reactive electrochemical polymerization of the precursor EDOT in aqueous solution. The SWCNT@SiO₂-PEDOT-PSS composite electrodes showed a heterogeneous rate constant more than three times higher than the electrode without conducting polymer. Similarly, the electroactive area was also enhanced to more than twice the area of SWCNT@SiO₂-modified electrodes. The morphology of the sample films was analyzed by scanning electron microscopy (SEM). Full article

(This article belongs to the Special Issue Conductive Polymers: Materials and Applications)

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22 pages, 5269 KiB

Open AccessArticle

Comparative Study of the Adsorption of Acid Blue 40 on Polyaniline, Magnetic Oxide and Their Composites: Synthesis, Characterization and Application

by Amir Muhammad, Anwar ul Haq Ali Shah and Salma Bilal

Materials 2019, 12(18), 2854; https://doi.org/10.3390/ma12182854 - 04 Sep 2019

Cited by 25 | Viewed by 2977

Abstract

Conducting polymers (CPs), especially polyaniline (PANI) based hybrid materials have emerged as very interesting materials for the adsorption of heavy metals and dyes from an aqueous environment due to their electrical transport properties, fascinating doping/de-doping chemistry and porous surface texture. Acid Blue 40 (AB40) is one of the common dyes present in the industrial effluents. We have performed a comparative study on the removal of AB40 from water through the application of PANI, magnetic oxide (Fe₃O₄) and their composites. Prior to this study, PANI and its composites with magnetic oxide were synthesized through our previously reported chemical oxidative synthesis route. The adsorption of AB40 on the synthesized materials was investigated with UV-Vis spectroscopy and resulting data were analyzed by fitting into Tempkin, Freundlich, Dubinin–Radushkevich (D–R) and Langmuir isotherm models. The Freundlich isotherm model fits more closely to the adsorptions data with R² values of 0.933, 0.971 and 0.941 for Fe₃O₄, PANI and composites, respectively. The maximum adsorption capacity of Fe₃O₄, PANI and composites was, respectively, 130.5, 264.9 and 216.9 mg g⁻¹. Comparatively good adsorption capability of PANI in the present case is attributed to electrostatic interactions and a greater number of H-bonding. Effect of pH of solution, temperature, initial concentration of AB40, contact time, ionic strength and dose of adsorbent were also investigated. Adsorption followed pseudo-second-order kinetics. The activation energy of adsorption of AB40 on Fe₃O₄, PANI and composites were 30.12, 22.09 and 26.13 kJmol⁻¹ respectively. Enthalpy change, entropy change and Gibbs free energy changes are −6.077, −0.026 and −11.93 kJ mol⁻¹ for adsorption of AB40 on Fe₃O₄. These values are −8.993, −0.032 and −19.87 kJ mol⁻¹ for PANI and −10.62, −0.054 and −19.75 kJ mol⁻¹ for adsorption of AB40 on PANI/Fe₃O₄ composites. The negative sign of entropy, enthalpy and Gibbs free energy changes indicate spontaneous and exothermic nature of adsorption. Full article

(This article belongs to the Special Issue Conductive Polymers: Materials and Applications)

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26 pages, 5891 KiB

Open AccessArticle

Enhanced Adsorptive Properties and Pseudocapacitance of Flexible Polyaniline-Activated Carbon Cloth Composites Synthesized Electrochemically in a Filter-Press Cell

by César Quijada, Larissa Leite-Rosa, Raúl Berenguer and Eva Bou-Belda

Materials 2019, 12(16), 2516; https://doi.org/10.3390/ma12162516 - 07 Aug 2019

Cited by 12 | Viewed by 3068

Abstract

Electrochemical polymerization is known to be a suitable route to obtain conducting polymer-carbon composites uniformly covering the carbon support. In this work, we report the application of a filter-press electrochemical cell to polymerize polyaniline (PAni) on the surface of large-sized activated carbon cloth (ACC) by simple galvanostatic electropolymerization of an aniline-containing H₂SO₄ electrolyte. Flexible composites with different PAni loadings were synthesized by controlling the treatment time and characterized by means of Scanning Electron microscopy (SEM), X-Ray Photoelectron Spectroscopy (XPS), physical adsorption of gases, thermogravimetric analysis (TGA), cyclic voltammetry and direct current (DC) conductivity measurements. PAni grows first as a thin film mostly deposited inside ACC micro- and mesoporosity. At prolonged electropolymerization time, the amount of deposited PAni rises sharply to form a brittle and porous, thick coating of nanofibrous or nanowire-shaped structures. Composites with low-loading PAni thin films show enhanced specific capacitance, lower sheet resistance and faster adsorption kinetics of Acid Red 27. Instead, thick nanofibrous coatings have a deleterious effect, which is attributed to a dramatic decrease in the specific surface area caused by strong pore blockage and to the occurrence of contact electrical resistance. Our results demonstrate that mass-production restrictions often claimed for electropolymerization can be easily overcome. Full article

(This article belongs to the Special Issue Conductive Polymers: Materials and Applications)

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26 pages, 5326 KiB

Open AccessArticle

Basic Blue Dye Adsorption from Water Using Polyaniline/Magnetite (Fe₃O₄) Composites: Kinetic and Thermodynamic Aspects

by Amir Muhammad, Anwar-ul-Haq Ali Shah, Salma Bilal and Gul Rahman

Materials 2019, 12(11), 1764; https://doi.org/10.3390/ma12111764 - 30 May 2019

Cited by 77 | Viewed by 5783

Abstract

Owing to its exciting physicochemical properties and doping–dedoping chemistry, polyaniline (PANI) has emerged as a potential adsorbent for removal of dyes and heavy metals from aqueous solution. Herein, we report on the synthesis of PANI composites with magnetic oxide (Fe₃O₄) for efficient removal of Basic Blue 3 (BB3) dye from aqueous solution. PANI, Fe₃O₄, and their composites were characterized with several techniques and subsequently applied for adsorption of BB3. Effect of contact time, initial concentration of dye, pH, and ionic strength on adsorption behavior were systematically investigated. The data obtained were fitted into Langmuir, Frundlich, Dubbanin-Rudiskavich (D-R), and Tempkin adsorption isotherm models for evaluation of adsorption parameters. Langmuir isotherm fits closely to the adsorption data with R² values of 0.9788, 0.9849, and 0.9985 for Fe₃O₄, PANI, and PANI/Fe₃O₄ composites, respectively. The maximum amount of dye adsorbed was 7.474, 47.977, and 78.13 mg/g for Fe₃O₄, PANI, and PANI/Fe₃O₄ composites, respectively. The enhanced adsorption capability of the composites is attributed to increase in surface area and pore volume of the hybrid materials. The adsorption followed pseudo second order kinetics with R² values of 0.873, 0.979, and 0.999 for Fe₃O₄, PANI, and PANI/Fe₃O₄ composites, respectively. The activation energy, enthalpy, Gibbs free energy changes, and entropy changes were found to be 11.14, −32.84, −04.05, and −0.095 kJ/mol for Fe₃O₄, 11.97, −62.93, −07.78, and −0.18 kJ/mol for PANI and 09.94, −74.26, −10.63, and −0.210 kJ/mol for PANI/Fe₃O₄ respectively, which indicate the spontaneous and exothermic nature of the adsorption process. Full article

(This article belongs to the Special Issue Conductive Polymers: Materials and Applications)

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16 pages, 6449 KiB

Open AccessArticle

Electrochemically Enhanced Drug Delivery Using Polypyrrole Films

by Sayed Ashfaq Ali Shah, Melike Firlak, Stuart Ryan Berrow, Nathan Ross Halcovitch, Sara Jane Baldock, Bakhtiar Muhammad Yousafzai, Rania M. Hathout and John George Hardy

Materials 2018, 11(7), 1123; https://doi.org/10.3390/ma11071123 - 01 Jul 2018

Cited by 62 | Viewed by 5935

Abstract

The delivery of drugs in a controllable fashion is a topic of intense research activity in both academia and industry because of its impact in healthcare. Implantable electronic interfaces for the body have great potential for positive economic, health, and societal impacts; however, the implantation of such interfaces results in inflammatory responses due to a mechanical mismatch between the inorganic substrate and soft tissue, and also results in the potential for microbial infection during complex surgical procedures. Here, we report the use of conducting polypyrrole (PPY)-based coatings loaded with clinically relevant drugs (either an anti-inflammatory, dexamethasone phosphate (DMP), or an antibiotic, meropenem (MER)). The films were characterized and were shown to enhance the delivery of the drugs upon the application of an electrochemical stimulus in vitro, by circa (ca.) 10–30% relative to the passive release from non-stimulated samples. Interestingly, the loading and release of the drugs was correlated with the physical descriptors of the drugs. In the long term, such materials have the potential for application to the surfaces of medical devices to diminish adverse reactions to their implantation in vivo. Full article

(This article belongs to the Special Issue Conductive Polymers: Materials and Applications)

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12 pages, 2635 KiB

Open AccessFeature PaperArticle

An Electrochemical Study on the Copolymer Formed from Piperazine and Aniline Monomers

by Samiha Dkhili, Sara López-Bernabeu, Chahineze Nawel Kedir, Francisco Huerta, Francisco Montilla, Salma Besbes-Hentati and Emilia Morallon

Materials 2018, 11(6), 1012; https://doi.org/10.3390/ma11061012 - 14 Jun 2018

Cited by 9 | Viewed by 3656

Abstract

A study on the electrochemical oxidation of piperazine and its electrochemical copolymerization with aniline in acidic medium is presented. It was found that the homopolymerization of piperazine cannot be achieved under electrochemical conditions. A combination of electrochemistry, in situ Fourier transform infrared (FTIR), and ex situ X-ray photoelectron spectroscopy (XPS) spectroscopies was used to characterize both the chemical structure and the redox behavior of an electrochemically synthesized piperazine–aniline copolymer. The electrochemical sensing properties of the deposited material were also tested against ascorbic acid and dopamine as redox probes. Full article

(This article belongs to the Special Issue Conductive Polymers: Materials and Applications)

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11 pages, 2291 KiB

Open AccessArticle

Silica Modified with Polyaniline as a Potential Sorbent for Matrix Solid Phase Dispersion (MSPD) and Dispersive Solid Phase Extraction (d-SPE) of Plant Samples

by Ireneusz Sowa, Magdalena Wójciak-Kosior, Maciej Strzemski, Jan Sawicki, Michał Staniak, Sławomir Dresler, Wojciech Szwerc, Jarosław Mołdoch and Michał Latalski

Materials 2018, 11(4), 467; https://doi.org/10.3390/ma11040467 - 22 Mar 2018

Cited by 18 | Viewed by 3881

Abstract

Polyaniline (PANI) is one of the best known conductive polymers with multiple applications. Recently, it was also used in separation techniques, mostly as a component of composites for solid-phase microextraction (SPME). In the present paper, sorbent obtained by in situ polymerization of aniline directly on silica gel particles (Si-PANI) was used for dispersive solid phase extraction (d-SPE) and matrix solid–phase extraction (MSPD). The efficiency of both techniques was evaluated with the use of high performance liquid chromatography with diode array detection (HPLC-DAD) quantitative analysis. The quality of the sorbent was verified by Raman spectroscopy and microscopy combined with automated procedure using computer image analysis. For extraction experiments, triterpenes were chosen as model compounds. The optimal conditions were as follows: protonated Si-PANI impregnated with water, 160/1 sorbent/analyte ratio, 3 min of extraction time, 4 min of desorption time and methanolic solution of ammonia for elution of analytes. The proposed procedure was successfully used for pretreatment of plant samples. Full article

(This article belongs to the Special Issue Conductive Polymers: Materials and Applications)

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25 pages, 11752 KiB

Open AccessArticle

Investigation of Polyaniline and a Functionalised Derivative as Antimicrobial Additives to Create Contamination Resistant Surfaces

by Julia Robertson, Marija Gizdavic-Nikolaidis and Simon Swift

Materials 2018, 11(3), 436; https://doi.org/10.3390/ma11030436 - 16 Mar 2018

Cited by 18 | Viewed by 4317

Abstract

Antimicrobial surfaces can be applied to break transmission pathways in hospitals. Polyaniline (PANI) and poly(3-aminobenzoic acid) (P3ABA) are novel antimicrobial agents with potential as non-leaching additives to provide contamination resistant surfaces. The activity of PANI and P3ABA were investigated in suspension and as part of absorbent and non-absorbent surfaces. The effect of inoculum size and the presence of organic matter on surface activity was determined. PANI and P3ABA both demonstrated bactericidal activity against Escherichia coli and Staphylococcus aureus in suspension and as part of an absorbent surface. Only P3ABA showed antimicrobial activity in non-absorbent films. The results that are presented in this work support the use of P3ABA to create contamination resistant surfaces. Full article

(This article belongs to the Special Issue Conductive Polymers: Materials and Applications)

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Review

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21 pages, 3559 KiB

Open AccessReview

Polyacetylene: Myth and Reality

by Bruce S. Hudson

Materials 2018, 11(2), 242; https://doi.org/10.3390/ma11020242 - 06 Feb 2018

Cited by 25 | Viewed by 6606

Abstract

Polyacetylene, the simplest and oldest of potentially conducting polymers, has never been made in a form that permits rigorous determination of its structure. Trans polyacetylene in its fully extended form will have a potential energy surface with two equivalent minima. It has been assumed that this results in bond length alternation. It is, rather, very likely that the zero-point energy is above the Peierls barrier. The experimental studies that purport to show bond alternation are reviewed and shown to be compromised by serious experimental inconsistencies or by the presence, for which there is considerable evidence, of finite chain polyenes. In this view, addition of dopants results in conductivity by facilitation of charge transport between finite polyenes. The double minimum potential that necessarily occurs for polyacetylene, if viewed as the result of elongation of finite chains, originates from admixture of the 1¹A_g ground electronic state with the 2¹A_g excited electronic singlet state. This excitation is diradical (two electron) in character. The polyacetylene limit is an equal admixture of these two ¹A_g states making theory intractable for long chains. A method is outlined for preparation of high molecular weight polyacetylene with fully extended chains that are prevented from reacting with neighboring chains. Full article

(This article belongs to the Special Issue Conductive Polymers: Materials and Applications)

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