Effect of Pb2+ and Cu2+ as a codopant on the structure,morphology and conductivity of nanostructured polyaniline

Polyaniline (PANI) has been successively synthesized in aqueous diethylene glycol solution medium by chemical oxidative polymerization of aniline using ammonium peroxidisulfate [(NH₄)₂S₂O₈] as an oxidant in an aqueous solution of 0.5 M acetic acid (CH₃COOH) as a dopant. Polyaniline–lead (PANI–Pb) and polyaniline–copper (PANI–Cu) nanocomposites have been chemically prepared for the first time by oxidative polymerization of aniline in aqueous diethylene glycol/acetic acidic medium. The synthesized PANI and nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR). Conductivity measurements of the polymer and nanocomposites were performed using the four-probe technique. Morphology changes of the composites were investigated by scanning electron microscopy (SEM). PANI nanotubes were formed without added codopant, but when Pb(CH₃COO)₂ or Cu(CH₃COO)₂ was added as a codopant, the morphology of PANI obviously changed. The PANI–Cu and PANI–Pb nanocomposites exhibit higher conductivity than the PANI homopolymer, but the conductivity of the composites slightly decreased on increasing the metal concentrations.     

Enhancement of electroconductivity of polyaniline/graphene oxide nanocomposites through in situ emulsion polymerization

The present study introduces a systematic approach to disperse graphene oxide (GO) during emulsion polymerization (EP) of Polyaniline (PANI) to form nanocomposites with improved electrical conductivities. PANI/GO samples were fabricated by loading different weight percents (wt%) of GO through modified in situ EP of the aniline monomer. The polymerization process was carried out in the presence of a functionalized protonic acid such as dodecyl benzene sulfonic acid, which acts both as an emulsifier and protonating agent. The microstructure of the PANI/GO nanocomposites was studied by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV–Vis spectrometry, Fourier transform infrared, differential thermal, and thermogravimetric analyses. The formed nanocomposites exhibited superior morphology and thermal stability. Meanwhile, the electrical conductivities of the nanocomposite pellets pressed at different applied pressures were determined using the four-probe analyzer. It was observed that the addition of GO was an essential component to improving the thermal stability and electrical conductivities of the PANI/GO nanocomposites. The electrical conductivities of the nanocomposites were considerably enhanced as compared to those of the individual PANI samples pressed at the same pressures. An enhanced conductivity of 474 S/m was observed at 5 wt% GO loading and an applied pressure of 6 t. Therefore, PANI/GO composites with desirable properties for various semiconductor applications can be obtained by in situ addition of GO during the polymerization process.     

Nanocomposite for methanol oxidation: synthesis and characterization of cubic Pt nanoparticles on graphene sheets

Abstract

We present our recent results on Pt nanoparticles on graphene sheets (Pt-NPs/G), a nanocomposite prepared with microwave assistance in ionic liquid 2-hydroxyethanaminiumformate. Preparation of Pt-NPs/G was achieved without the addition of extra reductant such as hydrazine or ethylene glycol. The Pt nanoparticles on graphene have a cubic-like shape (about 60 wt% Pt loading, Pt-NPs/G) and the particle size is 6 ± 3 nm from transmission electron microscopy results. Electrochemical cyclic voltammetry studies in 0.5 M aqueous H₂SO₄ were performed using Pt-NPs/G and separately, for comparison, using a commercially available electrocatalyst (60 wt% Pt loading, Pt/C). The electrochemical surface ratio of Pt-NPs/G to Pt/C is 0.745. The results of a methanol oxidation reaction (MOR) in 0.5 M aqueous H₂SO₄ + 1.0 M methanol for the two samples are presented. The MOR results show that the ratios of the current density of oxidation (I_f) to the current density of reduction (I_b) are 3.49 (Pt-NPs/G) and 1.37 (Pt/C), respectively, with a preference by 2.55 times favoring Pt-NPs/G. That is, the tolerance CO poisoning of Pt-NPs/G is better than that of commercial Pt/C.     

Synthesis and characterization of polyaniline nanorods/Ce(OH)3-Pr2O3/montmorillonite composites through reverse micelle template

Polyaniline (PANI) nanorods/Ce(OH)₃-Pr₂O₃/montmorillonite (MMT) nanocomposites were synthesized via in situ polymerization of aniline monomer through reverse micelle template (RMT) in the presence of montmorillonite and Ce(OH)₃, Pr₂O₃. In the experiment, sulphosalicylic acid was used as dopant, aniline was designated as oil phase and the aqueous solution comprising Ce³⁺ and Pr³⁺ as water phase. The nanocomposites were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD) analysis, Fourier transform infrared (FT-IR) spectroscopy and thermogravimetry-differential thermal analysis (TG-DTA). The results showed that PANI nanorods were synthesized in the interlayer spaces of MMT with uniform spherical rare earth nanoparticles. The thermal stability of the nanocomposites prepared was enhanced drastically compared with pure polyaniline.     

Composite QDs@MIP nanospheres for specific recognition and direct fluorescent quantification of pesticides in aqueous media

Quantum dots (QDs)-based molecularly imprinted polymer (MIP) composite nanospheres were successfully prepared via a facile and versatile ultrasonication-assisted encapsulation method. Unlike the hydrogen-bond-based MIPs, these so-prepared QDs-MIP composite nanospheres, relying on the interaction including van der Waals forces and hydrophobic forces, demonstrated excellent selectivity in aqueous media. Their small particle sizes and carboxyl-enriched polymer matrixes give rise to their good dispersibility and stability in aqueous solution, and faster adsorption and desorption kinetics, which further make them extensively applicable for chemical/biological sensors in aqueous media. Based on the fluorescence quenching via template analytes (diazinon) rebinding into the recognition cavities in the polymer matrixes, the QDs-MIP nanospheres were successfully applied to the direct fluorescence quantification of diazinon, independent of extracting templates from the MIP nanospheres, as well as further complicated and time-consuming assays. This novel method can selectively and sensitively detect down to 50 ng/mL of diazinon in water, and a linear relationship has been obtained covering the concentration range of 50-600 ng/mL. The present studies provide a new and general strategy to fabricate other multifunctional (luminescent and magnetic) inorganic-organic MIP nanocomposites with highly selective recognition ability in aqueous media and are pretty desirable for biomedical/chemical sensing applications.     

One-step synthesis of conductive graphene/polyaniline nanocomposites using sodium dodecylbenzenesulfonate: preparation and properties

The preparation of conducting graphene/polyaniline–sodium dodecylbenzenesulfonate (PANI–SDBS) nanocomposites using synthesised graphene as the starting material is successfully conducted in the present study. The effect of the anionic surfactant SDBS on the properties of the graphene/PANI–SDBS nanocomposites is studied. The structure and morphology of the synthesised nanocomposites are characterised by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, ultraviolet–visible (UV–vis) spectrophotometry, X-ray diffraction and atomic force microscopy (AFM). The electrical conductivity properties of the resulting nanocomposites are determined using a resistance meter measurement system. The FESEM and TEM images reveal that the addition of SDBS surfactant to the PANI transforms the nanofibers of the PANI to a nanosphere morphology of PANI–SDBS. FTIR and UV–vis studies reveal that the conductive graphene/PANI–SDBS nanocomposites are successfully synthesised. AFM characterisation shows that the addition of graphene reduces the root mean square roughness of the surface of the PANI. The electrical conductivity and thermal stability of the PANI are improved after the introduction of SDBS. The nanocomposites containing a 5 wt% graphene loading exhibit the highest electrical conductivity of 2.94?×?10^?2 S/cm, which is much higher than that of PANI (9.09?×?10^?6 S/cm).     

Comparatively electrochemical studies at different operational temperatures for the effect of layered silicate and spherical silica on the anticorrosion efficiency of PANI nanocomposite coatings

In this paper, a series of PANI nanocomposites have been successfully prepared by in situ oxidative polymerization. The as-prepared PANI nanocomposites were subsequently characterized by WAXRD patterns and TEM. It should be noted that the nanocomposite coating containing 3 wt-% of organophilic clay loading was found to exhibit an observable enhanced corrosion protection on cold-rolled steel (CRS) electrode at higher operational temperature of 50 degrees C, which was even better than that of uncoated and electrode-coated with PANI or PANI nanocomposites with 3 wt-% of amino-modified silica nanoparticles alone at room temperature of 30 degrees C based on the electrochemical parameter evaluations (e.g., E(corr), R(p), I(corr), R(corr) and impedance). The vapor permeability property at three different operational temperatures of PANI and PANI nanocomposite membranes were investigated by vapor permeability analyzer (VPA). Effect of material composition on the molecular weight, optical properties and surface hydrophobicity of neat PANI and PANI nanocomposite, in the form of membrane and solution, were studied by gel permeation chromatography (GPC), ultraviolet-visible absorption spectra and contact-angle measurements, respectively. Finally, electrical conductivity at three different operational temperatures of PANI and PANI nanocomposite powder-pressed pellets was also investigated through the measurements of standard four-point-probe technique.     

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.     

Synthesis of silver/silica nanocomposites anchored by polymer via in situ reduction

Silver/silica nanocomposites were synthesized by in situ reduction of silver salt and anchorage of the formed silver nanoparticles to silica nanospheres using a polymer anchor. Synthesis conditions including reductants, anchor polymers, and surfactants were determined. The successful formation of the nanocomposites was governed by the reduction of silver nitrate in citrate aqueous solution by sodium borohydride and adsorption onto polyvinylpyrrolidone coated silica nanospheres. The size and structure of the nanocomposites were observed by light scattering measurement and scanning electron microscopy, respectively. Optical properties of the nanocomposites were determined by UV-visible absorption spectra.     

Thermoelectric properties of porous multi-walled carbon nanotube/polyaniline core/shell nanocomposites

Porous polyaniline (PANI)-coated multi-walled carbon nanotube (MWNT) core/shell nanohybrids were fabricated through in situ polymerization and subsequently assembled into macroscopic composites. N(2) adsorption/desorption analysis indicated that the volume of nanopores increased significantly, which could make a significant contribution to phonon scattering. Thermal annealing was also carried out to improve the Seebeck coefficient of the as-produced nanocomposites. The optimal sample showed electrical conductivity of 14.1?S?cm(-1), a Seebeck coefficient of 79.8?μV K(-1) and thermal conductivity of 0.27?W?mK(-1), resulting in a highest figure of merit (ZT) of 0.01 at a very low loading of MWNTs (<1?wt%). These results will provide a potential direction to enhance thermoelectric performance of organic materials and also facilitate the application of organic materials in thermal energy harvesting or cooling.     

Preparation and application of magnetic cobalt/SiO2 core/shell nanospheres

Homogeneous SiO₂-coated cobalt nanospheres with tunable silica shell thickness from 21.7 nm to 4.5 nm were synthesized by using modified Stöber method. These nanocomposites were used as source materials to prepare SiO₂ semi-hollow and hollow nanospheres by partially and completely etching cobalt cores, respectively. A proposed formation mechanism of these Co/SiO₂ nanospheres with a core/shell structure was presented in this paper, which is also important for the rational design and synthesis of other monodisperse core/shell nanoarchitectures with uniform size and shape. Furthermore, these Co/SiO₂ nanospheres were also used as a substrate for the deposition of CdS nanocrystals to prepare magnetic luminescent Co/SiO₂/CdS nanocomposites.     

Polyaniline and polypyrrole modified conductive nanocomposites of polyfuran and polythiophene with montmorillonite clay

Nanocomposites of polyfuran (PF) and polythiophene (PTP) with montmorillonite clay (MMT) were prepared and modified by loading of polyaniline (PANI) and polypyrrole (PPY) moieties via polymerization of aniline (ANI) and pyrrole (PY) in aqueous dispersions of PF-MMT and PTP-MMT nanocomposites. Formation of PANI and PPY and their subsequent incorporation in the PF-MMT and PTP-MMT composites was confirmed by FTIR absorption studies. X-ray diffraction (XRD) patterns of PANI and PPY modified PF-MMT and PTP-MMT composites showed that PF-MMT and PTP-MMT intercalates were still present in the modified composites. Scanning electron microscopic analysis revealed distinctive morphological patterns of the various composite particles. The dc conductivity values of PANI and PPY modified PF-MMT and PTP-MMT composites were in the order of 10⁻² S/cm in either system – a value much improved compared to the same for both of the unmodified PF-MMT (10⁻⁷ S/cm) and PTP-MMT (10⁻⁵ S/cm) nanocomposites respectively.     

Water-soluble chitosan-quantum dot hybrid nanospheres toward bioimaging and biolabeling

A facile approach to prepare CdSe/ZnS quantum dot-encapsulated chitosan hybrid nanospheres (CS-QD) is developed by utilizing ethanol-aided counterion complexation in aqueous solution. The obtained CS-QD hybrid nanospheres have not only the loading space provided by the chitosan spherical matrix for loading multiply QDs but also unique fluorescent properties provided by the encapsulated QDs. Moreover, these hybrid nanospheres possess good biocompatibility and optical stability in physiological environment. It is demonstrated that CS-QD hybrid nanospheres can be internalized by tumor cells and hence act as labeling agent in cell imaging by optical microscopy. In addition, CS-QD hybrid nanospheres can be used for imaging of tumor in tumor-bearing mice via intratumoral administration and can accumulate at tumor site via the blood circulation based on intravenous injection. Thus, on the one hand, chitosan nanospheres provide the protection in both colloidal and optical stability arising from QDs and offer biocompatibility. On the other hand, the encapsulated QDs light up polymer nanospheres and display the fate of polymer nanospheres in cells and bodies.     

Monodisperse porphyrin nanospheres synthesized by coordination polymerization

Monodisperse nanospheres are formed by coordination polymerization tetrakis(4-pyridyl)porphyrin-metal complexes with chloroplatinic acid in aqueous solution. The porphyrin nanospheres and their platinized nanocomposites have potential applications in catalysis and solar energy conversion systems.     

Highly conductive graphene oxide/polyaniline hybrid polymer nanocomposites with simultaneously improved mechanical properties

Graphene oxide (GO) was added to a polymer composites system consisting of surfactant-wrapped/doped polyaniline (PANI) and divinylbenzene (DVB). The nanocomposites were fabricated by a simple blending, ultrasonic dispersion and curing process. The new composites show higher conductivity (0.02–9.8 S/cm) than the other reported polymer system filled with PANI (10⁻⁹–10⁻¹ S/cm). With only 0.45 wt% loading of GO, at least 29% enhancement in electric conductivity and 29.8% increase in bending modulus of the composites were gained. Besides, thermal stability of the composites was also improved. UV–Vis spectroscopy, X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) revealed that addition of GO improves the dispersion of PANI in the polymer composite, which is the key to realize high conductivity.     

Controlling the shapes and electrical conductivities of polyaniline-wrapped MWCNTs

Nanocomposites of carbon nanotubes with polyaniline (PANI) constitute promising conducting nanomaterials, due to their ease of synthesis, electrical conductivity, and environmental stability. Variously shaped multi-walled carbon nanotube (MWCNT)-PANI nanocomposites were synthesized, and their electrical conductivities were compared. This study shows that new synthetic methods were able to control the shapes and electrical conductivities of MWCNT-PANI nanocomposites. The shapes of the MWCNT-PANI nanocomposites were changed by altering the reactant concentrations and the sequence of adding the initiator, ammonium persulfate (APS). The use of surface-modified MWCNTs instead of pristine MWCNTs is also an important factor determining the shapes of the nanocomposites. It was found that the electrical conductivity is strongly dependent on the shape and PANI content. The electrical conductivities of the MWCNT-PANI nanocomposites increased when the PANI/MWCNT ratio was decreased. The nanocomposites were characterized via field emission transmission electron microscopy (FE-TEM), Fourier-transform infrared (FT-IR) and ultraviolet-visible (UV-Vis) spectroscopy, and elementary analysis of the MWCNT-PANI nanocomposites.     

Conducting polyaniline nanoparticles and their dispersion for waterborne corrosion protection coatings

A novel approach for preparing waterborne corrosion protection polyaniline (PANI)-containing coatings was developed. First, conducting polyaniline/partially phosphorylated poly(vinyl alcohol) (PANI/P-PVA) spherical nanoparticles with significant dispersibility in aqueous media were prepared by the chemical oxidative dispersion polymerization in presence of partially phosphorylated poly(vinyl alcohol) (P-PVA). The PANI/P-PVA-containing coatings with different PANI/P-PVA contents were then prepared, employing waterborne epoxy resin as the matrix. The corrosion protection property of PANI/P-PVA-containing coatings on mild steel was investigated by salt spray test and electrochemical impedance spectroscopy (EIS) technique in 3.0 wt % NaCl aqueous solution. The results indicated that the waterborne PANI/P-PVA-containing coatings (PANI/P-PVA content, 2.5 wt %) could offer high protection because the impedance values remained at higher than 1 × 10(7) Ω cm(2) after 30 days of salt spray tests. All the results were compared with these of the waterborne coatings containing PANI nanoparticles in the emeraldine salt form (PANI ES), and the protection mechanism was also proposed with the evidence of scanning electron microscope (SEM) and X-ray photoelectron spectrometry (XPS).     

Polyaniline/CuCl nanocomposites prepared by UV rays irradiation

In present paper, polynailine (PANI)/CuCl nanocomposites were prepared by UV rays irradiation method. In this method, photons in the UV rays and Cu²⁺ ions replaced conventional oxidant such as ammonium persulfate (APS) to promote polymerization of aniline monomer. The PANI/CuCl nanocomposites were characterized by infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscope (HRTEM), and electron diffraction (ED). The results indicated that aniline could polymerize to PANI by UV rays irradiation. Meanwhile, the results of HRTEM and ED confirmed that the CuCl dispersed into PANI was single crystal with cubic crystal structure. A potential formation mechanism of PANI/CuCl nanocomposites was investigated and suggested.     

Preparation of flake-like polyaniline/montmorillonite nanocomposites and their application for removal of Cr(VI) ions in aqueous solution

In this study, flake-like polyaniline/montmorillonite (PANI/MMT) nanocomposites with rough surface were successfully prepared by in situ chemical oxidation polymerization during which poly(2-acrylamido-2-methylpropanesulfonic acid), a polymer acid, on the surface of clay platelets was used as dopant of PANI and played a ‘bridge’ role to combine PANI with clay. Flake thickness and surface roughness of PANI/MMT composites decreased with the increase of montmorillonite/aniline feeding ratio. The effects of operating parameters including pH, contact time, Cr(VI) concentration, and adsorbent dose were studied. The pseudo-second-order equation and three adsorption isotherms including Langmuir, Freundlich, and Temkin equations were applied to determine the adsorption rate and capacity. The results show that the flake-like PANI/MMT nanocomposites exhibited a high adsorption capacity (167.5 mg/g). The excellent adsorption characteristic of flake-like PANI/MMT nanocomposites will render it a highly efficient and economically viable adsorbent for Cr(VI) removal.     

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.