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Conducting Polymer-Based Hybrid Nanomaterials

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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 (10 April 2021) | Viewed by 45037

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Dr. Srabanti Ghosh

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1. Department of Organic and Inorganic Chemistry, Universidad de Alcala (UAH), 28805 Madrid, Spain
2. Energy Material & Devices Division, CSIR - Central Glass and Ceramic Research Institute, Kolkata 700032, India
Interests: conducting polymer nanostructures; semiconductor nanomaterials, hybrid nanomaterials; photocatalysis; electrocatalysis; fuel cells; hydrogen generation; water splitting
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Dear Colleagues,

Conducting polymer-based nanohybrid (CPNHs) witnessed considerable progress due to their substantial advantages of earth abundant, facile modulation of electro-chemical properties through molecular engineering over the traditional inorganic materials. The hybridization of metals, carbon materials, inorganic semiconductors etc. with conducting polymer have been explored and continuing to grow with the objective of tuning the intrinsic properties of hybrid with multiple functionalities. Particularly CPNHs have received extensive attention in the field of energy conversion as well as storage application. CPNHs has revolutionized specific areas of catalysis such as pollutant removal, water splitting, hydrogen generation, electrochemical oxidation of organic molecule, and in other research and development in the energy domain.

The materials discovery together with state-of-the-art characterization technologies to identify new materials is a crucial aspect in energy research. This Special Issue on “Conducting Polymer-based Hybrid Nanomaterials” will address advances in experimental aspects of the synthesis, processing, characterization, properties of hybrid nanomaterials including the strategies to harvest solar light and electrochemical energy for possible application in catalysis, electrochemical oxidation of organic molecules, and electrochemical sensors etc. This special issue would ideally be guided by the fundamental scientific advances for the development of the next generation materials for photocatalytic solar fuel, sensors, environmental remedy and electrical power production.

Some examples can be found for the development of efficient strategies using conducting polymer nanostructures as support, revealing the pronounced impact on the metal-based nanostructures electrode with exceptionally high current density for fuel cell applications.

Another successful example can be found in conducting polymer based nanohybrids with nanowire, nanotube, and graphene for the application in photocatalysis and batteries.

This Focus Issue collects original research, comprehensive review papers, as well as communications from research groups with diverse backgrounds in conducting polymer-based nanohybrid to discuss all aspects of energy conversion and storage applications.

Dr. Srabanti Ghosh
Guest Editor

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Keywords

conducting polymer
nanostructure
nanohybrids
electrode materials
photocatalysis
electrocatalysis
fuel cells
H₂generation
batteries

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Published Papers (10 papers)

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Research

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14 pages, 2590 KiB

Open AccessArticle

Li-Nafion Membrane Plasticised with Ethylene Carbonate/Sulfolane: Influence of Mixing Temperature on the Physicochemical Properties

by Aigul S. Istomina, Tatyana V. Yaroslavtseva, Olga G. Reznitskikh, Ruslan R. Kayumov, Lyubov V. Shmygleva, Evgeny A. Sanginov, Yury A. Dobrovolsky and Olga V. Bushkova

Polymers 2021, 13(7), 1150; https://doi.org/10.3390/polym13071150 - 3 Apr 2021

Cited by 18 | Viewed by 4113

Abstract

The use of dipolar aprotic solvents to swell lithiated Nafion ionomer membranes simultaneously serving as electrolyte and separator is of great interest for lithium battery applications. This work attempts to gain an insight into the physicochemical nature of a Li-Nafion ionomer material whose phase-separated nanostructure has been enhanced with a binary plasticiser comprising non-volatile high-boiling ethylene carbonate (EC) and sulfolane (SL). Gravimetric studies evaluating the influence both of mixing temperature (25 to 80 °C) and plasticiser composition (EC/SL ratio) on the solvent uptake of Li-Nafion revealed a hysteresis between heating and cooling modes. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) revealed that the saturation of a Nafion membrane with such a plasticiser led to a re-organisation of its amorphous structure, with crystalline regions remaining practically unchanged. Regardless of mixing temperature, the preservation of crystallites upon swelling is critical due to ionomer crosslinking provided by crystalline regions, which ensures membrane integrity even at very high solvent uptake (≈200% at a mixing temperature of 80 °C). The physicochemical properties of a swollen membrane have much in common with those of a chemically crosslinked polymer gel. The conductivity of ≈10⁻⁴ S cm⁻¹ demonstrated by Li-Nafion membranes saturated with EC/SL at room temperature is promising for various practical applications. Full article

(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)

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11 pages, 3136 KiB

Open AccessArticle

Incorporating MXene into Boron Nitride/Poly(Vinyl Alcohol) Composite Films to Enhance Thermal and Mechanical Properties

by Seonmin Lee and Jooheon Kim

Polymers 2021, 13(3), 379; https://doi.org/10.3390/polym13030379 - 26 Jan 2021

Cited by 23 | Viewed by 4259

Abstract

Aggregated boron nitride (ABN) is advantageous for increasing the packing and thermal conductivity of the matrix in composite materials, but can deteriorate the mechanical properties by breaking during processing. In addition, there are few studies on the use of Ti₃C₂ MXene as thermally conductive fillers. Herein, the development of a novel composite film is described. It incorporates MXene and ABN into poly(vinyl alcohol) (PVA) to achieve a high thermal conductivity. Polysilazane (PSZ)-coated ABN formed a heat conduction path in the composite film, and MXene supported it to further improve the thermal conductivity. The prepared polymer composite film is shown to provide through-plane and in-plane thermal conductivities of 1.51 and 4.28 W/mK at total filler contents of 44 wt.%. The composite film is also shown to exhibit a tensile strength of 11.96 MPa, which is much greater than that without MXene. Thus, it demonstrates that incorporating MXene as a thermally conductive filler can enhance the thermal and mechanical properties of composite films. Full article

(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)

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16 pages, 6438 KiB

Open AccessArticle

Iridium and Ruthenium Modified Polyaniline Polymer Leads to Nanostructured Electrocatalysts with High Performance Regarding Water Splitting

by Razik Djara, Marie-Agnès Lacour, Abdelhafid Merzouki, Julien Cambedouzou, David Cornu, Sophie Tingry and Yaovi Holade

Polymers 2021, 13(2), 190; https://doi.org/10.3390/polym13020190 - 7 Jan 2021

Cited by 26 | Viewed by 4007

Abstract

The breakthrough in water electrolysis technology for the sustainable production of H₂, considered as a future fuel, is currently hampered by the development of tough electrocatalytic materials. We report a new strategy of fabricating conducting polymer-derived nanostructured materials to accelerate the electrocatalytic hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and water splitting. Extended physical (XRD, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX)) and electrochemical (cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS)) methods were merged to precisely characterize the as-synthesized iridium and ruthenium modified polyaniline (PANI) materials and interrogate their efficiency. The presence of Ir(+III) cations during polymerization leads to the formation of Ir metal nanoparticles, while Ru(+III) induces the formation of RuO₂ oxide nanoparticles by thermal treatment; they are therefore methods for the on-demand production of oxide or metal nanostructured electrocatalysts. The findings from using 0.5 M H₂SO₄ highlight an ultrafast electrochemical kinetic of the material PANI-Ir for HER (36 − 0 = 36 mV overpotential to reach 10 mA cm⁻² at 21 mV dec⁻¹), and of PANI-Ru for OER (1.47 − 1.23 = 240 mV overpotential to reach 10 mA cm⁻² at 47 mV dec⁻¹), resulting in an efficient water splitting exactly at its thermoneutral cell voltage of 1.45 V, and satisfactory durability (96 h). Full article

(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)

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13 pages, 3341 KiB

Open AccessArticle

Electrical Conductivity Based Ammonia Sensing Properties of Polypyrrole/MoS₂ Nanocomposite

by Sharique Ahmad, Imran Khan, Ahmad Husain, Anish Khan and Abdullah M. Asiri

Polymers 2020, 12(12), 3047; https://doi.org/10.3390/polym12123047 - 18 Dec 2020

Cited by 94 | Viewed by 4727

Abstract

Polypyrrole (PPy) and Polypyrrole/MoS₂ (PPy/MoS₂) nanocomposites were successfully prepared, characterized and studied for ammonia sensing properties. The as-prepared PPy and PPy/MoS₂ nanocomposites were confirmed by FTIR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction), SEM (scanning electron microscopy) and TEM (transmission electron microscopy) techniques. The ammonia sensing properties of PPy and PPy/MoS₂ nanocomposites were studied in terms of change in DC electrical conductivity on exposure to ammonia vapors followed by ambient air at room temperature. It was observed that the incorporation of MoS₂ in PPy showed high sensitivity, significant stability and excellent reversibility. The enhanced sensing properties of PPy/MoS₂ nanocomposites could be attributed to comparatively high surface area, appropriate sensing channels and efficiently available active sites. The sensing mechanism is explained on the basis of simple acid-base chemistry of polypyrrole. Full article

(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)

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18 pages, 8787 KiB

Open AccessArticle

Multifunctional Properties of Binary Polyrhodanine Manganese Ferrite Nanohybrids—From the Energy Converters to Biological Activity

by Emilia Zachanowicz, Magdalena Kulpa-Greszta, Anna Tomaszewska, Małgorzata Gazińska, Monika Marędziak, Krzysztof Marycz and Robert Pązik

Polymers 2020, 12(12), 2934; https://doi.org/10.3390/polym12122934 - 8 Dec 2020

Cited by 9 | Viewed by 2815

Abstract

The PRHD@MnFe₂O₄ binary hybrids have shown a potential for applications in the biomedical field. The polymer cover/shell provides sufficient surface protection of magnetic nanoparticles against adverse effects on the biological systems, e.g., it protects against Fenton’s reactions and the generation of highly toxic radicals. The heating ability of the PRHD@MnFe₂O₄ was measured as a laser optical density (LOD) dependence either for powders as well as nanohybrid dispersions. Dry hybrids exposed to the action of NIR radiation (808 nm) can effectively convert energy into heat that led to the enormous temperature increase ΔT 170 °C (>190 °C). High concentrated colloidal suspensions (5 mg/mL) can generate ΔT of 42 °C (65 °C). Further optimization of the nanohybrids amount and laser parameters provides the possibility of temperature control within a biologically relevant range. Biological interactions of PRHD@MnFe₂O₄ hybrids were tested using three specific cell lines: macrophages (RAW 264.7), osteosarcoma cells line (UMR-106), and stromal progenitor cells of adipose tissue (ASCs). It was shown that the cell response was strongly dependent on hybrid concentration. Antimicrobial activity of the proposed composites against Escherichia coli and Staphylococcus aureus was confirmed, showing potential in the exploitation of the fabricated materials in this field. Full article

(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)

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14 pages, 5071 KiB

Open AccessArticle

Preparation of Polyvinyl Alcohol (PVA)-Based Composite Membranes Using Carboxyl-Type Boronic Acid Copolymers for Alkaline Diffusion Dialysis

by Lizhen Peng, Xiaonan Huang, Dandan Liu, Jibin Miao, Bin Wu, Ming Cao, Qianqian Ge, Bin Yang, Lifen Su, Ru Xia, Zhengzhi Zheng, Peng Chen and Jiasheng Qian

Polymers 2020, 12(10), 2360; https://doi.org/10.3390/polym12102360 - 14 Oct 2020

Cited by 6 | Viewed by 3011

Abstract

Carboxyl-type boronic acid copolymers (CBACs) were synthesized by a radical polymerization method and used for the preparation of polyvinyl alcohol (PVA)-based composite membranes via a solution mixture method. The as-prepared composite membranes exhibited a water uptake (W_R) of 122.6–150.0%, an ion exchange capacity (IEC) of 0.0147–0.0518 mmol g⁻¹, and excellent mechanical (elongation at break (E_b) of 103.8–148.4%, tensile strength (TS) of 38.7–58.6 MPa) and thermal stability. The alkali resistances of the as-prepared membranes were tested by immersing the samples into 2 mol L⁻¹ NaOH solutions at 25 °C for 60 h, and the results were encouraging: the mass loss and swelling degree of the as-prepared membranes were in the ranges of 1.9–5.9% and 222.6–241.9%, respectively. The separation performances of the as-prepared membranes were evaluated by the diffusion dialysis (DD) process with an NaOH/Na₂WO₄ mixture at room temperature. The results demonstrated that the dialysis coefficients of hydroxide (U_OH) were in the range of 0.0147–0.0347 m h⁻¹, and the separation factors (S) were in the range of 29.5–62.6. The introduced carboxyl groups from CBACs and the –OH groups from PVA were both deemed to play significant roles in the promotion of ion transport: the –COO⁻ groups formed negatively charged transport channels for Na⁺ by electrostatic attraction, and the –OH groups promoted the transport of OH⁻ via hydrogen bonding. Full article

(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)

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11 pages, 4430 KiB

Open AccessEditor’s ChoiceArticle

Semiconducting Properties of the Hybrid Film of Elastic Poly(styrene-b-butadiene-b-styrene) Block Copolymer and Semiconducting Poly(3-hexylthiophene) Nanofibers

by Takanori Goto, Jun Morita, Yuya Maekawa, Shinji Kanehashi and Takeshi Shimomura

Polymers 2020, 12(9), 2118; https://doi.org/10.3390/polym12092118 - 17 Sep 2020

Cited by 2 | Viewed by 2815

Abstract

We investigated the electrical properties of a composite film loaded with semi-conductive poly(3-hexylthiophene) (P3HT) nanofibers dispersed in poly(styrene-b-butadiene-b-styrene) (SBS). This structure can be regarded as the hybrid of SBS matrix with elastic mechanical properties and P3HT nanofibers with semiconducting properties. The P3HT nanofibers were embedded in the fingerprint pattern of microphase-separated SBS, as observed by scanning force microscopy. Furthermore, the electrical conductivity and field-effect mobility of the composite films were evaluated. The field-effect mobility was estimated to be 6.96 × 10⁻³ cm² V⁻¹ s⁻¹, which is consistent with the results of previous studies on P3HT nanofibers dispersed in an amorphous polymer matrix including poly(methyl methacrylate) and polystyrene, and we found that the P3HT nanofiber network was connected in the SBS bulk matrix. The film was stretchable; however, at elongation by two times, the nanofiber network could not follow the elongation of the SBS matrix, and the conductivity decreased drastically. The field-effect transistor of this film was operated by bending deformation with a radius of curvature of 1.75 cm, though we could not obtain an off-state and the device operated in a normally-on state. Full article

(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)

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18 pages, 8345 KiB

Open AccessArticle

Synthesis and Electrorheological Response of Graphene Oxide/Polydiphenylamine Microsheet Composite Particles

by Chun Yan Gao, Min Hwan Kim, Hyoung-Joon Jin and Hyoung Jin Choi

Polymers 2020, 12(9), 1984; https://doi.org/10.3390/polym12091984 - 31 Aug 2020

Cited by 8 | Viewed by 2690

Abstract

Conducting graphene oxide/polydiphenylamine (GO/PDPA) microsheet nanocomposite particles were fabricated via in-situ oxidative polymerization using diphenylamine in the presence of GO. The morphological structures and dimensions of the fabricated GO/PDPA composites were evaluated using transmission electron microscopy and scanning electron microscopy. Electrorheological (ER) responses and creep behaviors of an ER fluid consisting of the GO/PDPA composites when suspended in silicone oil were evaluated using a rotational rheometer under input electric field. Three different types of yield stresses were examined along with dielectric analysis, demonstrating their actively tunable ER behaviors. Full article

(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)

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Review

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28 pages, 2508 KiB

Open AccessReview

Advances in Molecularly Imprinted Polymers Based Affinity Sensors (Review)

by Simonas Ramanavicius, Arunas Jagminas and Arunas Ramanavicius

Polymers 2021, 13(6), 974; https://doi.org/10.3390/polym13060974 - 22 Mar 2021

Cited by 155 | Viewed by 9311

Abstract

Recent challenges in biomedical diagnostics show that the development of rapid affinity sensors is very important issue. Therefore, in this review we are aiming to outline the most important directions of affinity sensors where polymer-based semiconducting materials are applied. Progress in formation and development of such materials is overviewed and discussed. Some applicability aspects of conducting polymers in the design of affinity sensors are presented. The main attention is focused on bioanalytical application of conducting polymers such as polypyrrole, polyaniline, polythiophene and poly(3,4-ethylenedioxythiophene) ortho-phenylenediamine. In addition, some other polymers and inorganic materials that are suitable for molecular imprinting technology are also overviewed. Polymerization techniques, which are the most suitable for the development of composite structures suitable for affinity sensors are presented. Analytical signal transduction methods applied in affinity sensors based on polymer-based semiconducting materials are discussed. In this review the most attention is focused on the development and application of molecularly imprinted polymer-based structures, which can replace antibodies, receptors, and many others expensive affinity reagents. The applicability of electrochromic polymers in affinity sensor design is envisaged. Sufficient biocompatibility of some conducting polymers enables to apply them as “stealth coatings” in the future implantable affinity-sensors. Some new perspectives and trends in analytical application of polymer-based semiconducting materials are highlighted. Full article

(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)

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19 pages, 3790 KiB

Open AccessReview

Conducting Polymer-Based Nanohybrids for Fuel Cell Application

by Srabanti Ghosh, Suparna Das and Marta E. G. Mosquera

Polymers 2020, 12(12), 2993; https://doi.org/10.3390/polym12122993 - 15 Dec 2020

Cited by 60 | Viewed by 6269

Abstract

Carbon materials such as carbon graphitic structures, carbon nanotubes, and graphene nanosheets are extensively used as supports for electrocatalysts in fuel cells. Alternatively, conducting polymers displayed ultrahigh electrical conductivity and high chemical stability havegenerated an intense research interest as catalysts support for polymer electrolyte membrane fuel cells (PEMFCs) as well as microbial fuel cells (MFCs). Moreover, metal or metal oxides catalysts can be immobilized on the pure polymer or the functionalized polymer surface to generate conducting polymer-based nanohybrids (CPNHs) with improved catalytic performance and stability. Metal oxides generally have large surface area and/or porous structures and showed unique synergistic effects with CPs. Therefore, a stable, environmentally friendly bio/electro-catalyst can be obtained with CPNHs along with better catalytic activity and enhanced electron-transfer rate. The mass activity of Pd/polypyrrole (PPy) CPNHs as an anode material for ethanol oxidation is 7.5 and 78 times higher than that of commercial Pd/C and bulk Pd/PPy. The Pd rich multimetallic alloys incorporated on PPy nanofibers exhibited an excellent electrocatalytic activity which is approximately 5.5 times higher than monometallic counter parts. Similarly, binary and ternary Pt-rich electrocatalysts demonstrated superior catalytic activity for the methanol oxidation, and the catalytic activity of Pt₂₄Pd₂₆Au₅₀/PPy significantly improved up to 12.5 A per mg Pt, which is approximately15 times higher than commercial Pt/C (0.85 A per mg Pt). The recent progress on CPNH materials as anode/cathode and membranes for fuel cell has been systematically reviewed, with detailed understandings into the characteristics, modifications, and performances of the electrode materials. Full article

(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)

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