Synthesis of polyaniline/ZrO<Subscript>2</Subscript> nanocomposites and their performance in AC conductivity and electrochemical supercapacitance

Polyaniline/zirconium oxide (PANI/ZrO₂) nanocomposites have been synthesized by incorporating ZrO₂ nanoparticles into the PANI matrix via liquid–liquid interfacial polymerization method. The composite formation and structural changes in PANI/ZrO₂ nanocomposites were investigated by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). PXRD pattern of PANI/ZrO₂ nanocomposites exhibited sharp and well-defined peaks of monoclinic phase of ZrO₂ in PANI matrix. SEM images of the composites showed that ZrO₂ nanoparticles were dispersed in the PANI matrix. The FT-IR analysis revealed that there was strong interaction between PANI and ZrO₂. AC conductivity and dielectric properties of the nanocomposites were studied in the frequency range, 50–10⁶ Hz. AC conductivity of the nanocomposites obeyed the power law indicating the universal behaviour of disordered media. The nanocomposites showed high dielectric constant in the order of 10⁴, which could be related to dielectric relaxation phenomenon. Further, the materials were checked for their supercapacitance performance by using cyclic voltammetry (CV), chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS). Among the synthesized nanocomposites, PANI/ZrO₂-25 wt.% showed a higher specific capacitance of 341 F g^?1 at 2 m Vs^?1 and good cyclic stability with capacitance retention of about 88% even after 500 charge–discharge cycles.     

Rod-shaped polyaniline-barium ferrite nanocomposite: preparation, characterization and properties

Rod-shaped polyaniline (PANI)-barium ferrite nanocomposite was synthesized by in situ polymerization of aniline in the presence of BaFe(12)O(19) nanoparticles with diameters of 60-80?nm. The structure, morphology and properties of the nanocomposite were measured using powder x-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and vibrating sample magnetometry. Different ferrite/PANI ratios were selected in order to study magnetic and conductive properties. The results indicated that there were some interactions between PANI chains and ferrite particles. The saturation magnetization and the coercivity varied with the ferrite content. The conductivity at room temperature decreased from 43.35 to 6.9 × 10(-2)?S?cm(-1) when the ferrite content changed from 0 to 50?wt%. The composite has excellent electromagnetic parameters which indicates potential application in high performance adsorbing materials in broadband and high frequency ranges. The polymerization mechanism and interactions in the nanocomposites were also studied.     

Novel surfactant-stabilized graphene-polyaniline composite nanofiber for supercapacitor applications

In this work, we present a new synthesis method for surfactant stabilized graphene (SSG) combined with polyaniline nanofiber (PANI-Nf) and apply the composite material as supercapacitor (SC) electrodes by screen-printing technique. Surfactant stabilized graphene polyaniline nanofiber composite (PANI-SSG) was synthesized by electrolytic exfoliation of graphite and subsequent interfacial polymerization. Firstly, graphite was electrolytically exfoliated in an electrolyte containing anionic surfactant. Next, ammonium peroxydisulfate initiator and hydrochloric acid were added to the graphene dispersion to form the aqueous phase for interfacial polymerization of polyaniline nanofiber. This dispersion was then added to the water-insoluble solvent phase containing aniline monomer. The polymerization only occurred at the interface of the two immiscible phases leading to polyaniline nanofiber decorated graphene structures. Characterizations by scanning electron microscopy, transmission electron microscopy, atomic force microscopy and Raman spectroscopy suggested nanocomposite formation with intermolecular π-π bonding of graphene with polyaniline nanofibers. Pastes of the materials were screen printed on stainless steel current collectors and tested for SC performance by cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD) measurements with 2 M H₂SO₄ electrolyte using a home-built two-electrode test-cell. CV results showed redox peaks of polyaniline with wide cyclic loop, indicating large pseudocapacitance of the nanocomposite. From GCD measurement, a high specific capacitance of 690 Fg⁻¹ at 1 Ag⁻¹ was achieved. Therefore, PANI-SSG nano-composite prepared by electrolytic exfoliation and interfacial polymerization is a promising candidate for SC applications.     

A novel multi-walled carbon nanotube (MWNT)-based nanocomposite for PEFC electrodes

A novel nanocomposite comprising MWNTs and mixed-conducting polymeric components (electronic and ionic) is prepared, characterized and investigated as a support for platinum (Pt). Nanocomposite of MWNTs and poly (3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT?CPSS) is prepared by in situ polymerization and characterized using Fourier?CTransform infrared spectroscopy (FT?CIR), thermogravimetric analysis (TGA) in conjunction with scanning electron microscopy (SEM). Atomic force microscopy (AFM) studies are also carried out to characterize the surface topography of MWNTs/PEDOT?CPSS nanocomposite. X-ray diffraction (XRD) studies reveal that MWNTs/PEDOT?CPSS nanocomposite provides better backbone for the improved dispersion of Pt as evidenced by the reduced Pt crystallite size over MWNTs/PEDOT?CPSS nanocomposite compared to MWNTs. Electrochemical characterization studies performed with Pt/nanocomposite and Pt/MWNTs demonstrate the superior catalytic activity of Pt/nanocomposite under reduced Nafion loadings in relation to Pt/MWNTs. It is observed that mixed conducting nanoporous network of MWNTs/PEDOT?CPSS composite structure promotes the catalytic activity of Pt by enhancing catalyst utilization.     

Graphene oxide-filled conducting polyaniline composites as methanol-sensing materials

Polyaniline/graphene oxide (PANI/GO) composites were prepared by polymerization of aniline monomer in the presence of GO under acidic conditions. The synthesized samples were characterized by Fourier transform infra red spectroscopy, ultraviolet–visible absorption, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and thermogravimetric analysis. The direct current electrical conductivity of the composite was calculated by a four-probe technique. It is found that the conductivity dramatically increased to 241 S m^?1 for PANI/GO (5 wt%) composite at 110 °C compared to pure PANI (7.5 S m^?1). The composite material was investigated as a methanol vapour sensor and compared with pure PANI. The methanol-sensing characteristics of the prepared composite was monitored by measuring the change in electrical resistivity on exposure to methanol vapour at different concentrations. The resistivity of PANI increases on exposure to methanol vapour because of strong hydrogen bonding between methanol with the polymer chain. A density functional theory study was carried out to verify the proposed concept of hydrogen bonding between the polymer chains and methanol. The presence of GO in PANI/GO composite increases the sensitivity towards methanol as compared with the pure PANI.     

Hydrophilic behaviour of gold-poly (o-phenylenediamine) hybrid nanocomposite

An in situ synthesis route is described for the preparation of a gold-poly (o-phenylenediamine) nanocomposite material by the interfacial polymerization route. The synthesis was carried out at the organic–aqueous interface. It was found that polymerization of o-phenylenediamine (PDA) using HAuCl₄ as an oxidizing agent leads to the formation of poly-PDA with a fiber-like morphology, while the reduction of HAuCl₄ results in the formation of well dispersed and stabilized gold nanoparticles within the polymer matrix. The resultant composite material was purely hydrophilic in nature and was deposited in the aqueous fraction of the reaction medium. The metal–polymer was characterized by means of different techniques, such as UV–vis and Raman spectroscopy that provided information about the chemical structure of polymer, whereas electron microscopy images provided information regarding the morphology of the composite material and the distribution of the metal particles in the composite material.     

Fabrication and characterization of polyaniline-znO hybrid nanocomposite thin films

Polyaniline (PANI)-ZnO nanocomposite thin film has been successfully fabricated on glass substrates by using vacuum deposition technique. The as-grown PANI-ZnO nanocomposite thin films have been characterized using X-ray diffraction, Scanning Electron Microscopy, Atomic Force Microscopy, UV-visible spectrophotometer and Fourier Transform Infrared (FTIR) spectroscopy, respectively. X-ray diffraction of as-grown film shows the reflection of ZnO nanoparticles along with a broad peak of PANI. The surface morphology of nanocomposite films has been investigated using scanning electron microscopy and atomic force microscopy. The hypsochromic shift of the UV absorption band corresponding to pi-pi* transition in polymeric chain of PANI and a band at 504 cm(-1) due to ZnO nanoparticles has been observed in the FTIR spectra. The hydrogen bonding between the imine group of PANI and ZnO nanoparticle has been confirmed from the presence of the absorbance band at 1151 cm(-1) in the FTIR spectra of the nanocomposite thin films.     

One-pot synthesis of Polyindole–Au nanocomposite and its nanoscale electrical properties

Nanosized gold (Au) and polyindole (PIn) composite was prepared via in-situ polymerization of indole, using metal salt chloro-auric acid as an oxidant, in a microemulsion system. The oxidization of indole and the reduction of Au³⁺ ions occurred simultaneously in a single step, which resulted in a core shell structure having a coating of polyindole over monodispersed, size-controlled, highly populated, and stable gold nanoparticles. Indole polymerization governed by chloro-auric acid, was monitored using UV–vis absorption spectroscopy. Nanoscale electrical characterization of polyindole nanocomposite was performed using current-sensing atomic force microscopy. The investigated properties of the composite proved its enormous potential in electronic applications and fabrication of nanoscale organic devices.     

Microstructure,electrical and humidity sensing properties of TiO<Subscript>2</Subscript>/polyaniline nanocomposite films prepared by sol–gel spin coating technique

High sensitive resistive type humidity sensor based titanium oxide/polyaniline (TiO₂/PANI) nanocomposite thin films prepared by a sol–gel spin coating technique on an alumina substrate. The resultant nanocomposites were characterized by using X-ray diffraction (XRD), Field emission electron microscopy, Fourier transform infrared spectroscopy (FTIR), UV–Vis absorbance and energy dispersive spectra analysis. In the XRD patterns of both pure and TiO₂/PANI composite confirms the deposition of PANI on TiO₂ and the average size of the composite particle was found to be 32 nm. Large number of nano grain surface being covered by PANI, which agrees very well with the results obtained by XRD studies. FTIR and UV–Vis spectra reveal that the PANI component undergoes an electronic structure modification as a result of the TiO₂ and PANI interaction. The room temperature resistivity was found to be for TiO₂ and TiO₂/PANI nanocomposite films 1.42?×?10⁶ and 2.56?×?10³ Ω cm respectively. The obtained TiO₂/PANI nanocomposites sensor exhibited higher humidity sensing performance such as high sensitivity, fast response (20 s) and recovery time (15 s) and high stability.     

Preparation and characterization of polyaniline/exfoliated graphite composite via a combination method of in situ polymerization and thermal expansion

Polyaniline/exfoliated graphite (PANI/EG) composite was prepared via a combination method of in situ polymerization and thermal expansion and characterized, using scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). In the in situ polymerization, PANI/graphite intercalation compounds (GIC) composite was synthesized by GIC and aniline. In the thermal expansion, PANI/EG composite was prepared by PANI/GIC composite. The characterization showed that the morphology of PANI/EG composite was analogous to foam and the surface of PANI/EG composite had many micro-apertures. When PANI/GIC composite was synthesized by 0.80 g of GIC and 2.00 g of aniline, PANI/GIC composite would be exfoliated to PANI/EG composite at 200 °C, which had 75.00 mL·g⁻¹ of the expansion volume and 0.01Ω⁻¹ cm⁻¹of the conductivity.     

Investigation of solar-induced photoelectrochemical water splitting and photocatalytic dye removal activities of camphor sulfonic acid doped polyaniline-WO_3-MWCNT ternary nanocomposite

The camphor sulfonic acid doped polyaniline-WO_3-multiwall carbon nanotube(CSA PANI-WO_3-CNT)ternary nanocomposite was synthesized during in-situ oxidative polymerization and characterized by Fourier transform infrared(FTIR) spectroscopy, Raman spectroscopy, X-ray diffraction(XRD), Field emission scanning electron microscopy(FESEM), X-ray photoelectron spectroscopy(XPS), Transmission electron microscopy(TEM), and Energy-dispersive X-ray spectroscopy(EDS). The application of CSA PANIWO_3-CNT ternary nanocomposite was investigated as the photocatalyst in the degradation of methylene blue dye(MB) and as the noble metal-free photoanode in photoelectrochemical water splitting under solar light irradiation. The degradation percentage of MB dye after 60 min illumination by CSA PANI-WO_3-CNT ternary nanocomposite reached 91.40% which was higher than that of pure WO_3(43.45%), pure CSA PANI(48.4%) and CSA PANI-WO_3 binary nanocomposite(85.15%). The photocurrent density of indium tin oxide(ITO)/CSA PANI-WO_3-CNT photoanode obtained 0.81 m A/cm~2 at 1.23 V vs. reversible hydrogen electrode under illumination which was 1.27, 2.13, and 4.26 times higher than that of the ITO/CSA PANI-WO_3(0.64 m A/cm~2), ITO/pure CSA PANI(0.38 m A/cm~2), and ITO/pure WO_3(0.19 m A/cm~2). Also,the applied bias photon-to-current efficiency(ABPE) of ITO/CSA PANI-WO_3-CNT was obtained 0.11%which showed two-fold, four-fold, and five-fold enhancements compared to the ITO/CSA PANI-WO_3,ITO/CSA PANI, and ITO/WO_3, respectively. The electrochemical impedance spectroscopy, as well as the Mott-Schottky results, confirmed the better photoelectrocatalytic activity of ITO/CSA PANI-WO_3-CNT in comparison with ITO/WO_3, ITO/CSA PANI, and ITO/CSA PANI-WO_3. The observed improvement in the photocatalytic and photoelectrocatalytic performances of WO_3 in the presence of CSA PANI is due to the formation of type-II heterojunction between WO_3 and CSA PANI which allows the separation of charge carriers easier and faster. On the other hand, MWCNT addition to the CSA PANI-WO_3 nanocomposite provided the conducting substrate for efficient interfacial charge separation as well as transferring.     

Preparation of new antimony(0)/polyaniline nanocomposites by a one-pot solution phase method

The new Sb(0)/PANI nanocomposite was successfully synthesized by a one-pot solution phase method. Sb(0) particles were first prepared by the reduction of SbCl₅ or SbCl₃ using t-BuONa-activated NaH in THF. A ligand exchange with aniline on t-BuONa-stabilized Sb(0) particles yielded aniline-stabilized particles. The Sb(0)/PANI nanocomposite was finally obtained by polymerizing aniline-stabilized Sb(0) particles by using ammonium persulfate. The morphology and the structure of the nanocomposite was examined by transmission electron microscopy (TEM), selected-area electron diffraction (SAED), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Results obtained show that the Sb(0) precursor has a great influence on the size and the crystallinity of Sb(0) nanoparticles dispersed in PANI.     

Preparation, characterization and photocatalytic activity of TiO2/polyaniline core-shell nanocomposite

Polyaniline (PANI) as a promising conducting polymer has been used to prepare polyaniline/TiO₂ (PANI/TiO₂) nanocomposite with core-shell structure as photocatalyst. Titanium dioxide (TiO₂) nanoparticles with an average crystal size of 21?nm were encapsulated by PANI via the in situ polymerization of aniline on the surface of TiO₂ nanoparticles. FT?CIR, UV-Vis-NIR, XRD, SEM and TEM techniques were used to characterize the PANI/TiO₂ core-shell nanocomposite. Photocatalytic activity of PANI/TiO₂ nanocomposite was investigated under both UV and visible light irradiations and compared with unmodified TiO₂ nanoparticles. Results indicated deposition of PANI on the surface of TiO₂ nanoparticles which improved the photocatalytic activity of pristine TiO₂ nanoparticles.     

Facile synthesis of papillae-like polyaniline nanocones on graphene nanosheets for ultracapacitors

Papillae-like polyaniline (PANI) nanocones arrays growing on graphsene nanosheets (GNs) were synthesized in mass at low cost by in situ polymerization with the assistant of ethanol. Scanning electron microscopy and transmission electron microscopy images show that papillae-like PANI nanocones arrays are located uniformly on flexible two-dimensional GNs. Electrochemical properties are tested by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. The electrochemical performances of GNs/PANI hybrid are better than those of bare GNs or PANI. GNs/PANI electrode delivered a maximum specific capacitance of 372 F g^?1 at a current density of 0.1 A g^?1 in 1.0 M Na₂SO₄ aqueous solution. And the composite exhibit an excellent cycle life with ~80% specific capacitance retention over 3000 cycles at 1 A g^?1. The GNs/PANI nanocomposites will be one of the most promising flexible electrode materials for high-performance ultracapacitors.     

Nanocomposites based on rutile-TiO2 and polyaniline

A polyaniline/rutile-TiO₂ nanocomposite, with a conductivity of 0.5 S cm^− 1 at 25 °C, was prepared by in-situ polymerization of aniline in the presence of rutile-TiO₂ nanoparticles, and was characterized by Fourier-transform infrared spectra, wide-angle X-ray diffraction, transmission electron microscopy, conductivity and cyclic voltammetry, as well as thermogravimetric analysis. The introduction of conducting polyaniline (PANI), not only improved the conductivity of rutile-TiO₂ nanoparticles, but also improved the dispersibility of rutile-TiO₂ nanoparticles. It can potentially be used in commercial applications as fillers for antistatic and anticorrosion coatings.     

Large-scale preparation of polyaniline nanospheres anchored with thiol-stabilized gold nanoparticles

Reported herein is the preparation of a new nanostructured composite consisting of PANI(SH) (where PANI(SH) is poly(aniline-co-4-aminothio phenol)) and gold nanoparticles (AuNPs)) via "seed"-induced bulk polymerization. The PANI(SH)-AuNPs composite was designated as PANI(SH)-Au-NS(P). The composite was characterized in terms of its morphology and structural, thermal, and electrochemical properties. The field emission scanning electron microscopy (FESEM) image of PANI(SH)-Au-NS(P) revealed the presence of PANI(SH) nanospheres (sizes: approximately 150-250 nm) with finely distributed AuNPs (approximately 10 nm). The usefulness of PANI(SH)-Au-NS(P) as an electrocatalyst towards the oxidation of methanol was tested.     

Nanocomposite synthesis by absorption of nanoparticles into macroporous hydrogels. Building a chemomechanical actuator driven by electromagnetic radiation

Macroporous hydrogels irreversibly absorb solid nanoparticles from aqueous dispersions. A nanocomposite is made using a macroporous thermosensitive hydrogel (poly(N-isopropylacrylamide-co-(2-acrylamido-2-methyl propane sulfonic acid)) (poly(NIPAm-co-AMPS)) and conductive polymer (polyaniline, PANI) nanoparticles (PANI NPs). Macroporous gels of poly(NIPAm-co-AMPS) were made by a cryogelation technique. NPs of PANI were produced by precipitation polymerization. It is found that PANI NPs are easily absorbed into the macroporous hydrogels while conventional non-porous hydrogels do not incorporate NPs. It is shown that PANI NPs, dispersed in water, absorb NIR laser light or microwave radiation, increasing their temperature. Upon irradiation of the nanocomposite with microwaves or NIR laser light, the PANI NPs heat up and induce the phase transition of the thermosensitive hydrogel matrix and the internal solution is released. Other nano-objects, such as gold nanorods and PANI nanofibers, are also easily incorporated into the macroporous gel. The resulting nanocomposites also suffer a phase transition upon irradiation with electromagnetic waves. The results suggest that, using a thermosensitive matrix and conducting nanoparticles, mechanical/chemical actuators driven at a distance by electromagnetic radiation can be built. The sensitivity of the nanocomposite to electromagnetic radiation can be modulated by the pH, depending on the nature of the incorporated nanoparticles. Additionally, it is possible to make systems which absorb either NIR or microwaves or both.     

Enhancing the thermoelectric performance by defect structures induced in p-type polypyrrole-polyaniline nanocomposite for room-temperature thermoelectric applications

Organic thermoelectric materials mainly conducting polymers are green materials that can convert heat energy into electrical energy and vice versa at room temperature. In the present work, we investigated the thermoelectric properties of polymer nanocomposite of polypyrrole (PPy) and polyaniline (PANI) (PPy/PANI) by varying the pyrrole: aniline monomer ratios (60:40, 50:50, and 40:60). The PPy/PANI composite is prepared by in-situ chemical polymerization of PPy on PANI dispersion. It has been observed that the combination of two conducting polymers has enhanced the electrical and thermal properties in the PPy/PANI composite due to the strong π–π stacking and H-bonding interaction between the conjugated structure of PPy and conjugated structure of PANI. The maximum electrical conductivity of 14.7 S m^?1 was obtained for composite with high pyrrole content, whereas the maximum Seebeck coefficient of 29.5 μV K^?1 was obtained for composite with high aniline content at 366 K. Consequently, the PPy/PANI composite with pyrrole to aniline monomer ratio of 60:40 exhibits the optimal electrical conductivity, Seebeck coefficient, and high power factor. As a result, the maximum power factor of 2.24 nWm^?1 K^?2 was obtained for the PPy/PANI composite at 60:40 pyrrole to aniline monomer ratio, which is 29 times and 65.8 times higher than PPy (0.077 nWm^?1 K^?2) and PANI (0.034 nWm^?1 K^?2), respectively.

     

Amperometric biosensor based on carbon nanotubes coated with polyaniline/dendrimer-encapsulated Pt nanoparticles for glucose detection

A novel amperometric glucose biosensor based on the nanocomposites of multi-wall carbon nanotubes (CNT) coated with polyaniline (PANI) and dendrimer-encapsulated Pt nanoparticles (Pt-DENs) is prepared. CNT coated with protonated PANI is in situ synthesized and Pt-DENs is absorbed on PANI/CNT composite surface by self-assembly method. Then Glucose oxidase (GOx) is crosslink-immobilizated onto Pt-DENs/PANI/CNT composite film. The results show that the fabricated GOx/Pt-DENs/PANI/CNT electrode exhibits excellent response performance to glucose, such as low detection limit (0.5 µM), wide linear range (1 µM–12 mM), short response time (about 5 s), high sensitivity (42.0 µA mM^? 1 cm^? 2) and stability (83% remains after 3 weeks).     

Structural and magnetic properties of nanocomposites based on nanostructured polyaniline and titania nanotubes

Nanocomposites consisting of self-assembled polyaniline (PANI) nanostructures and titania nanotubes (TiO₂-NT) were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous dispersion of TiO₂-NT (outer diameter ~10 nm), without added acid. The influence of initial mole ratio of aniline to TiO₂ (80, 20, and 5) on the morphology, electrical conductivity, molecular structure, crystallinity, and magnetic properties of synthesized PANI/TiO₂ nanocomposites was studied. Transmission electron microscopy, Raman spectroscopy, and X-ray powder diffraction proved that the shape and structure of TiO₂-NT in the final nanocomposites were preserved. The shape of PANI nanostructures formed in the nanocomposites was influenced by the initial aniline/TiO₂-NT mole ratio. Nanotubes and nanorods are predominant PANI nanostructures in the nanocomposite prepared with the highest aniline/TiO₂ mol ratio of 80. The decrease of aniline/TiO₂ molar ratio induced more pronounced formation of nanorod network. The electrical conductivity of PANI/TiO₂ nanocomposites was in the range (1.3–2.4) × 10^?3 S cm^?1. The nanocomposites exhibit weak ferromagnetic behavior. Approximately order of magnitude lower values of coercive field and remanent magnetization were obtained for nanocomposite samples in comparison to pure PANI.