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Cutting Edge Research on the Electrochemistry of Intrinsically Conducting Polymers - Celebrating the Honorary Retirement of Prof. Dr. Rudolf Holze: A Renowned Polymer Electrochemist

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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Applications".

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 34977

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Prof. Dr. Salma Bilal

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1. Karlsruhe Institute of Technology (KIT), Institute for Applied Materials – Electrochemical Technologies (IAM-ET), 76131 Karlsruhe, Germany
2. National Center of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan
Interests: synthesis, characterization and electrochemical applications of intrinsically conducting polymers; supercapacitors; corrosion; sensors
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Prof. Dr. Yuping Wu

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Cochair of IUPAC International Conference on Novel Materials and Their Synthesis (NMS)(www.nms-iupac.org) Dean, School of Energy Science and Engineering, Nanjing Tech University, Nanjing 211816, China
Interests: material characterization; electrochemistry; energy storage; batteries; electrodes
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Dr. Deepak Dubal

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School of Chemistry and Physics, Faculty of Science, Queensland University of Technology, Gardens Point Campus, Brisbane, QLD 4000, Australia
Interests: energy conversion and storage; battery recycling; nanogenerators
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Prof. Dr. Anwar ul Haq Ali Shah

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Institute of Chemical Science, University of Peshawar, Peshawar 25120, Pakistan
Interests: conducting polymers; spectroelectrochemistry; electrochemistry; energy storage; sensors; fuel cells; computational chemistry
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Special Issue Information

Dear Colleagues,

Intrinsically conducting polymers are a prospective class of advanced materials capable of conducting electricity due to partial oxidation or reduction. They possess an extended π-conjugation along the polymer backbone and exhibit semiconducting behavior, hence creating a promising field of research. These polymers have received significant attention from both scientific and engineering communities because of their unique electrical and optical properties previously exhibited by only inorganic systems (e.g., silicon, copper, liquid mercury). Their distinctive features, such as the electrical conductivity of metals and mechanical properties associated with conventional polymers, led them to gain the name “Synthetic Metals”. Chemists and physicists who dreamed of replacing metals in electronic devices with lightweight and cheap materials, got their hopes up with the discovery of these polymers.

This Special Issue is dedicated to Prof. Dr. Rudolf Holze, on the occasion of his honorary retirement, as an acknowledgment of his contributions towards understanding the electrochemistry of intrinsically conducting polymers. Research articles and review papers are welcomed on the synthesis of intrinsically conducting polymers, novel developments on understanding their electrochemical properties, along with the applications in the field of sensors, biosensors, corrosion protection, light emitting diodes, energy storage and conversion, wearable electronics, and so on.

Prof. Salma Bilal
Prof. Dr. Yupping Wu
Dr. Deepk Dubal
Prof. Dr. Anwar ul Haq Ali Shah
Guest Editors

Manuscript Submission Information

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.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

intrinsically conducting polymers
synthesis and electrochemical applications of intrinsically conducting polymers
energy storage and conversion
corrosion
sensors/biosensors
wearable electronics
light-emitting diodes

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Published Papers (7 papers)

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Research

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19 pages, 4282 KiB

Open AccessArticle

Performance Improvement of Gold Electrode towards Methanol Electrooxidation in Akaline Medium: Enhanced Current Density Achieved with Poly(aniline-co-2-hydroxyaniline) Coating at Low Overpotential

by Anwar ul Haq Ali Shah, Sadaf Zia, Gul Rahman and Salma Bilal

Polymers 2022, 14(2), 305; https://doi.org/10.3390/polym14020305 - 13 Jan 2022

Cited by 4 | Viewed by 2170

Abstract

Electronically conducting poly (aniline-co-2-hydroxyaniline) (PACHA), a copolymer of aniline and 2-hydroxyaniline (2HA), was electrochemically coated on gold substrate for methanol electrooxidation in alkaline media. The electrochemical behavior of PACHA coated gold electrode towards methanol electrooxidation was investigated via cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) for application in an alkaline fuel cell. Methanol electrooxidation was observed at two different electrode potentials depending on the concentration of the base. At the PACHA coated gold electrode, the methanol oxidation peak was observed at lower overpotential (at 0.19 V) in a solution of high base concentration (1.8 M NaOH), which was 30 mV lower than the peak for the uncoated gold electrode. In addition, the Faradic current Imax obtained on the PACHA coated electrode (20 mA) was two times higher as compared to the Faradic current Imax of the un-modified gold electrode (10 mA). In solution of lower base concentration (0.06 M NaOH), the electrooxidation of methanol became sluggish on both electrodes, as indicated by peak shifting towards positive potential and with reduced faradaic current (at 0.74 V on PACHA coated electrode; Imax 10 mA). The electrooxidation of methanol at both lower and higher electrode potentials was analyzed mechanistically and discussed in light of the literature. EIS results were interpreted using Nyquist and Bode plots. The charge transfer resistance was decreased and pseudo-capacitive behavior changed to conductive behavior when external applied potential was increased from 0.1 V to 0.4 V. Full article

(This article belongs to the Special Issue Cutting Edge Research on the Electrochemistry of Intrinsically Conducting Polymers - Celebrating the Honorary Retirement of Prof. Dr. Rudolf Holze: A Renowned Polymer Electrochemist)

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20 pages, 3636 KiB

Open AccessArticle

Physical, Chemical, and Electrochemical Properties of Redox-Responsive Polybenzopyrrole as Electrode Material for Faradaic Energy Storage

by Bushra Begum, Salma Bilal, Anwar ul Haq Ali Shah and Philipp Röse

Polymers 2021, 13(17), 2883; https://doi.org/10.3390/polym13172883 - 27 Aug 2021

Cited by 17 | Viewed by 2904

Abstract

Polybenzopyrrole (Pbp) is an emerging candidate for electrochemical energy conversion and storage. There is a need to develop synthesis strategies for this class of polymers that can help improve its overall properties and make it as suitable for energy storage applications as other well-studied polymers in this substance class, such as polyaniline and polypyrrole. In this study, by synthesizing Pbp in surfactant-supported acidic medium, we were able to show that the physicochemical and electrochemical properties of Pbp-based electrodes are strongly influenced by the respective polymerization conditions. Through appropriate optimization of various reaction parameters, a significant enhancement of the thermal stability (up to 549.9 °C) and the electrochemical properties could be achieved. A maximum specific capacitance of 166.0 ± 2.0 F g⁻¹ with an excellent cycle stability of 87% after 5000 cycles at a current density of 1 A g⁻¹ was achieved. In addition, a particularly high-power density of 2.75 kW kg⁻¹ was obtained for this polybenzopyrrole, having a gravimetric energy density of 17 Wh kg⁻¹. The results show that polybenzopyrroles are suitable candidates to compete with other conducting polymers as electrode materials for next-generation Faradaic supercapacitors. In addition, the results of the current study can also be easily applied to other systems and used for adaptations or new syntheses of advanced hybrid/composite Pbp-based electrode materials. Full article

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13 pages, 2925 KiB

Open AccessArticle

Synthesis and Characterization of Polyaniline-Chitosan Patches with Enhanced Stability in Physiological Conditions

by Sami Ur Rahman, Salma Bilal and Anwar ul Haq Ali Shah

Polymers 2020, 12(12), 2870; https://doi.org/10.3390/polym12122870 - 30 Nov 2020

Cited by 25 | Viewed by 4346

Abstract

Electroconductive polymeric patches are being developed in the hope to interface with the electroresponsive tissues. For these constructs, conjugated polymers are considered as conductive components for their electroactive nature. Conversely, the clinical applications of these conductive polymeric patches are limited due to their short operational time, a decrease in their electroactivity occurs with the passage of time. This paper reports on the polymerization of aniline on prefabricated chitosan films on microscopic glass slides in the presence of sodium phytate. The strong chelation among sodium phytate, aniline and chitosan led to the formation of electoconductive polymeric patch. We assume that immobilization of sodium phytate in the polymeric patch helps to prevent electric deterioration, extend its electronic stability and reduce sheet resistance. The patch oxidized after three weeks (21 days) of incubation in phosphate buffer (pH 7.4 as physiological medium). This feasible fabrication technique set the foundation to design electronically stable, conjugated polymer-based patches, by providing a robust system of conduction that could be used with electroactive tissues such as cardiac muscles at the interface. Full article

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18 pages, 2276 KiB

Open AccessArticle

Synthesis, Optical, Thermal and Structural Characteristics of Novel Thermocleavable Polymers Based on Phthalate Esters

by Ary R. Murad, A. Iraqi, Shujahadeen B. Aziz, Sozan N. Abdullah and Rebar T. Abdulwahid

Polymers 2020, 12(12), 2791; https://doi.org/10.3390/polym12122791 - 25 Nov 2020

Cited by 9 | Viewed by 3327

Abstract

In this work three novel phthalate-based thermocleavable copolymers, PBTP-11, PBTDTP-11 and PFDTP-11 have been designed and synthesized. PBTP-11 and PBTDTP-11 were prepared by copolymerizing distannylated bithiophene without or with flanked thienyl groups as the electron-donor units with dibrominated secondary phthalate ester as the electron-acceptor units. PFDTP-11 was prepared by copolymerizing distannylated fluorene flanked by thienyl groups as the electron-donor moieties with dibrominated secondary phthalate ester as the electron-acceptor moieties. All polymers were prepared via the Stille polymerization. The impact of two different electron-donor units on the solubility, molecular weights, optical properties, thermal and structural properties of the resulting polymers were investigated. PFDTP-11 had the highest average molecular weight (M_n = 16,400 g mol⁻¹). The polymers had E_g in the range of 2.11–2.58 eV. After thermal treatment, the E_g of the polymers were reduced by around 0.3–0.4 eV. This significant control over bandgap is promising and opens a gate towards commercializing these copolymers in energy harvesting devices such as solar cells. TGA data showed weight loss at around 300 °C, corresponding to the elimination of the secondary ester groups. After annealing, the soluble precursor polymers were transformed into active phthalic anhydride polymers and the resulting films were completely insoluble in all solvents, which shows good stability. Powder XRD studies showed that all polymers have an amorphous nature in the solid state, and therefore can be employed as electrolytes in energy devices. Full article

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19 pages, 2552 KiB

Open AccessArticle

An Amazingly Simple, Fast and Green Synthesis Route to Polyaniline Nanofibers for Efficient Energy Storage

by Sami ur Rahman, Philipp Röse, Anwar ul Haq Ali Shah, Ulrike Krewer and Salma Bilal

Polymers 2020, 12(10), 2212; https://doi.org/10.3390/polym12102212 - 27 Sep 2020

Cited by 25 | Viewed by 3789

Abstract

The major drawbacks of the conventional methods for preparing polyaniline (PANI) are the large consumptions of toxic chemicals and long process durations. This paper presents a remarkably simple and green route for the chemical oxidative synthesis of PANI nanofibers, utilizing sodium phytate as a novel and environmentally friendly plant derived dopant. The process shows a remarkable reduction in the synthesis time and usage of toxic chemicals with good dispersibility and exceedingly high conductivity up to 10 S cm⁻¹ of the resulting PANI at the same time. A detailed characterization of the PANI samples has been made showing excellent relationships between their structure and properties. Particularly, the electrochemical properties of the synthesized PANI as electrode material for supercapacitors were analyzed. The PANI sample, synthesized at pre-optimized conditions, exhibited impressive supercapacitor performance having a high specific capacitance (C_sp) (832.5 Fg⁻¹ and 528 Fg⁻¹ at 1 Ag⁻¹ and 40 Ag⁻¹, respectively) as calculated from galvanostatic charge/discharge (GCD) curves. A good rate capability with a capacitance retention of 67.6% of its initial value was observed. The quite low solution resistance (R_s) value of 281.0 × 10⁻³ Ohm and charge transfer resistance value (R_ct) of 7.44 Ohm represents the excellence of the material. Further, a retention of 95.3% in coulombic efficiency after 1000 charge discharge cycles, without showing any significant degradation of the material, was also exhibited. Full article

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21 pages, 5574 KiB

Open AccessArticle

Reduced Graphene Oxide/Poly(Pyrrole-co-Thiophene) Hybrid Composite Materials: Synthesis, Characterization, and Supercapacitive Properties

by Anwar ul Haq Ali Shah, Sami Ullah, Salma Bilal, Gul Rahman and Humaira Seema

Polymers 2020, 12(5), 1110; https://doi.org/10.3390/polym12051110 - 13 May 2020

Cited by 21 | Viewed by 4328

Abstract

Reduced graphene oxide/poly(pyrrol-co-thiophene) (RGO/COP), prepared by facile in-situ oxidative copolymerization, is reported as a new hybrid composite material with improved supercapacitance performance as compared to the respective homopolymers and their composites with RGO. The as-prepared hybrid materials were characterized with ultraviolet–visible (UV–Vis) spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray (EDX) analysis. The electrochemical behavior and energy storage properties of the materials were tested by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrostatic impedance spectroscopy (EIS) techniques in 0.5 M H₂SO₄. The specific capacitance (Csp) for RGO/COP calculated from the CV curve was 467 F/g at a scan rate of 10 mV/s. While the Csp calculated from the GCD was 417 F/g at a current density of 0.81 A/g. The energy density calculated was 86.4 Wh/kg with a power density of 630 W/kg. The hybrid composite exhibits good cyclic stability with 65% capacitance retention after 1000 cycles at a scan rate of 100 mV/s. The present work brings a significance development of RGO/COP composites to the electrode materials for pseudocapacitive application. Full article

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Review

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47 pages, 9849 KiB

Open AccessReview

Conducting Polymers for Optoelectronic Devices and Organic Solar Cells: A Review

by Ary R. Murad, Ahmed Iraqi, Shujahadeen B. Aziz, Sozan N. Abdullah and Mohamad A. Brza

Polymers 2020, 12(11), 2627; https://doi.org/10.3390/polym12112627 - 9 Nov 2020

Cited by 159 | Viewed by 12811

Abstract

In this review paper, we present a comprehensive summary of the different organic solar cell (OSC) families. Pure and doped conjugated polymers are described. The band structure, electronic properties, and charge separation process in conjugated polymers are briefly described. Various techniques for the preparation of conjugated polymers are presented in detail. The applications of conductive polymers for organic light emitting diodes (OLEDs), organic field effect transistors (OFETs), and organic photovoltaics (OPVs) are explained thoroughly. The architecture of organic polymer solar cells including single layer, bilayer planar heterojunction, and bulk heterojunction (BHJ) are described. Moreover, designing conjugated polymers for photovoltaic applications and optimizations of highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy levels are discussed. Principles of bulk heterojunction polymer solar cells are addressed. Finally, strategies for band gap tuning and characteristics of solar cell are presented. In this article, several processing parameters such as the choice of solvent(s) for spin casting film, thermal and solvent annealing, solvent additive, and blend composition that affect the nano-morphology of the photoactive layer are reviewed. Full article

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Cutting Edge Research on the Electrochemistry of Intrinsically Conducting Polymers - Celebrating the Honorary Retirement of Prof. Dr. Rudolf Holze: A Renowned Polymer Electrochemist

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