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.     

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.     

Organic-inorganic hybrid materials based on polyaniline/TiO(2) nanocomposites for ascorbic acid fuel cell systems

Polyaniline was grafted onto a mixture of rutile and anatase TiO(2) nanoparticles by in situ chemical oxidative polymerization. These nanocomposites were characterized by carbon, hydrogen and nitrogen (CHN) analysis, x-ray diffraction (XRD), Fourier transform infrared (FTIR), ultraviolet-visible (UV-vis), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis. FTIR and UV-vis confirm the formation of polyaniline on TiO(2) nanoparticles. The TEM shows that the composites consist of PANI and TiO(2) nanoparticles. Compared to the neat polyaniline, PANI/TiO(2) composites show a higher capacitance and also a higher activity per mass of polyaniline. Since the PANI/TiO(2) composites are stable during the electrooxidation of ascorbic acid, they can be used as an alternative catalyst for direct ascorbic acid fuel cells.     

Humidity sensing behaviour of polyaniline/magnesium chromate (MgCrO<Subscript><Emphasis Type="Bold">4</Emphasis></Subscript>) composite

‘In situ’ polymerization of polyaniline (PANI) was carried out in the presence of magnesium chromate (MgCrO ₄ ) to synthesize PANI/ceramic (MgCrO ₄ ) composite. These prepared composites were characterized by XRD, FTIR and SEM, which confirm the presence of MgCrO ₄ in polyaniline matrix. The temperature dependent conductivity measurement shows the thermally activated exponential behaviour of PANI / MgCrO ₄ composites. The decrease in electrical resistance was observed when the polymer composites were exposed to the broad range of relative humidity (ranging between 20 and 95% RH). This decrease is due to increase in surface electrical conductivity resulting from moisture absorption and due to capillary condensation of water causing change in conductivity within the sensing materials. PANI / MgCrO ₄ composites are found to be sensitive to low humidity ranging from 20 to 50 % RH.     

Effect of different carbon fillers and dopant acids on electrical properties of polyaniline nanocomposites

Electrically conducting nanocomposites of polyaniline (PANI) with carbon-based fillers have evinced considerable interest for various applications such as rechargeable batteries, microelectronics, sensors, electrochromic displays and light-emitting and photovoltaic devices. The nature of both the carbon filler and the dopant acid can significantly influence the conductivity of these nanocomposites. This paper describes the effects of carbon fillers like carbon black (CB), graphite (GR) and muti-walled carbon nanotubes (MWCNT) and of dopant acids like methane sulfonic acid (MSA), camphor sulfonic acid (CSA), hydrochloric acid (HCl) and sulfuric acid (H₂SO₄) on the electrical conductivity of PANI. The morphological, structural and electrical properties of neat PANI and carbon–PANI nanocomposites were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT–IR), UV–Vis spectroscopy and the four-point probe technique, respectively. Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) studies were also conducted for different PANI composites. The results show that PANI and carbon–PANI composites with organic acid dopants show good thermal stability and higher electrical conductivity than those with inorganic acid dopants. Also, carbon–PANI composites generally show higher electrical conductivity than neat PANI, with highest conductivities for PANI–CNT composites. Thus, in essence, PANI–CNT composites prepared using organic acid dopants are most suitable for conducting applications.     

High conductivity and low percolation threshold in polyaniline/graphite nanosheets composites

An easy process for the synthesis of polyaniline/graphite nanosheets (PANI/NanoG) composites was developed. NanoG were prepared by treating the expanded graphite with sonication in aqueous alcohol solution. Scanning electron microscopy (SEM), X-ray diffraction techniques (XRD), Fourier transform infrared (FT-IR), and transmission electron microscopy (TEM) were used to characterize the structures of NanoG and PANI/NanoG conducting composites. Electrical conductivity measurements indicated that the percolation threshold of PANI/NanoG composites at room temperature was as low as 0.32 vol.% and the conductivity of PANI/NanoG composites was 420 S/cm. The percolation theory, mean-field theory, and excluded volume theory were applied to interpret the conducting properties. Results showed that the low value of percolation threshold may be mainly attributed to nanoscale structure of NanoG forming conducting bridge in PANI matrix and there exists contact resistance in the percolation network formed within PANI/NanoG composites.     

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.     

Preparation and characterization of conducting polyaniline/silica nanosheet composites

A series of polyaniline/silica nanosheet composites (PANI/SNS) with different contents of the silica nanosheets derived from vermiculite via acid-leaching were prepared via the in situ chemical oxidation polymerization. The PANI/SNS composites were characterized with Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and electrical conductivity measurement. It is interesting that the electrical conductivities of the PANI/SNS composites increased with the increasing of the contents of the silica nanosheets added because of the moisture absorption. It was confirmed by the TGA analysis.     

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.     

Synthesis of a soluble polyaniline–ferrite composite: magnetic and electric properties

We report the preparation of a processible magnetite/polyaniline (Fe₃O₄/PANI) nanocomposite, containing dodecylbencensulfonic acid (DBSA) as a surfactant and dopant, with both magnetic and conducting properties. Different amounts of Fe₃O₄ nanoparticles were successfully disposed with FeCl₃ solution to prevent their aggregation in the solution by the application of common ion effect. The magnetic properties of the resulting composites were investigated by a quantum design magnetometer (PMPS). The (Fe₃O₄/PANI) nanocomposite showed at 300 K no loop of hysteresis indicating the superparamagnetic nature. The saturation magnetization varies from 0.167 to 28.45 emu/g with increasing Fe₃O₄ content. Zero field cooling (ZFC) and Field cooling (FC) profiles showed that the polyaniline matrix allows each ferrite nanoparticles to behave independently and interparticle interactions are not important for iron oxide content lower than 36 wt.%. The electrical conductivity of composites was found to be higher than that of the pure PANI in spite of the insertion of the insulating material Fe₃O₄ particles. It is noticeable that conductivity increases with low Fe₃O₄ particles content and then decreases. Structural characterization by X-ray diffraction (XRD), UV spectroscopy and thermogravimetric analysis (TGA) have been performed.     

Synthesis, characterization and magnetic properties of polyaniline/γ-Fe2O3 composites

Conducting polyaniline/γ-Fe₂O₃ (PANI/FE) composites have been synthesized using an in situ deposition technique by placing fine-graded γ-Fe₂O₃ in a polymerization mixture of aniline. The composites are characterized by using scanning electron microscopy (SEM), X-ray diffraction (XRD) and infrared (IR) spectroscopy. The electrical properties such as d.c. and a.c. conductivities are studied by sandwitching the pellets of these composites between the silver electrodes. It is observed that the conductivity increases up to a composition of 20 wt.% of γ-Fe₂O₃ in polyaniline and decreases thereafter. The initial increase in conductivity is attributed to the extended chain length of polyaniline, where polarons possess sufficient energy to hop between favourable sites. Beyond 20 wt.% of γ-Fe₂O₃ in polyaniline, the blocking of charge carrier hop occurs, reducing conductivity values. The magnetic properties such as hysteresis characteristics and normalized a.c. susceptibility are also measured, which show a strong dependence on content of γ-Fe₂O₃ in polyaniline. Because of superparamagnetic behaviour of these composites, they may find extensive technological applications, especially for absorbing and shielding applications in microwave frequencies.     

Alkylated graphene nanosheet composites with polyaniline nanofibers

We demonstrate a simple method to prepare alkylated graphene/polyaniline composites (a-GR/PANI) using solution mixing of exfoliated alkyl Iodododecane treated graphene oxide sheets with polyaniline nanofiber; polyaniline nanofibers (PANI) prepared by using rapid mixing polymerization significantly improve the processibility of polyaniline and its performance in many conventional applications. Also, polyaniline nanofibers exhibit excellent water dispersibility due to their uniform nanofiber morphology. Morphological study using SEM and TEM analysis showed that the fibrous PANI in the composites a-GR/PANI mainly adsorbed onto the surface or intercalated between the graphene sheets, due especially to the good interfacial interaction between the alkylated gaphene and the polyaniline nanofibers. The existence of polyaniline nanofibers on the surface of the garphene and the alkylated graphene sheets was confirmed by using FT-IR, FT-Raman and X-ray diffraction analysis. Due to the good interfacial interaction between the alkylated graphene and the polyanilines nanofibers, the composite (a-GR/PANI) exhibited excellent dispersion stability in DMF compared to the same composite (GR/PANI) without alkylation. The electrical conductivity of the (GR/PANI) composite was 9% higher than that of pure PANI and the same weight percent for the composite after alkylation was 13% higher than that of pure PANI nanofibers.     

Dielectric relaxation and ac conductivity of polyaniline–zinc ferrite composite

In situ polymerization of aniline is carried out in the presence of zinc ferrite to synthesize polyaniline/ZnFe₂O₄ composites (PANI/ZnFe₂O₄) by chemical oxidation method. The composite has been synthesized with various compositions (10, 20, 30, 40 and 50 wt.%) of zinc ferrite in PANI. From the infrared spectroscopy (FTIR) studies on polyaniline/ZnFe₂O₄ composites, the peak at 1140 cm^?1 is considered to be measure of the degree of electron delocalization. The surface morphology of these composites is studied with scanning electron micrograph (SEM). The ac conductivity and dielectric properties are studied in the frequency range from 10² to 10⁶ Hz. The results obtained for these composites are of scientific and technological interest.     

Synthesis and characterization of metallic nanoparticles and their incorporation into electroconductive polymer composites

Gold and copper–gold nanoparticles were synthesized using anionic microemulsions as reducing reactors. The microemulsions were prepared using sodium bis(2-ethylhexyl)sulfosuccinate (Aerosol OT) and copper(II) bis(2-ethylhexyl)sulfosuccinate (Cu(AOT)₂) as surfactants, which were dissolved in isooctane containing an appropriate quantity of water. The growth of nanoparticles was monitored by UV/vis spectroscopy and the nanoparticles formed were characterized by transmission electron microscopy (TEM). The metallic nanoparticles were incorporated into films of an electroconductive polymer (ECP) composite: polyaniline-poly(n-butyl methacrylate) (PANI/PBMA) by the casting technique. The nanoparticle-ECP composite films were characterized by scanning electron microscopy (SEM), electrical conductivity measurements and NH₄OH and H₂O₂-sensing capability experiments. The inclusion of nanoparticles results in a cooperative phenomena between the polyaniline and the nanoparticles and as a consequence, the gold nanoparticles increased the electrical conductivity of the ECP film by two orders of magnitude.     

Synthesis and electrorheological properties of polyaniline/silicon dioxide composites

This study was to synthesize the inherently conductive polymer polyaniline using an optimized process to prepare polyaniline/silicon dioxide (PANI/SiO₂) composites by in situ polymerization and ex situ solution mixing. PANI and PANI/SiO₂ composite films were prepared by drop-by-drop and spin-coating methods. The morphology of particles and films were examined by a scanning electron microscope (SEM). SEM measurements indicated that the SiO₂ were well-dispersed and isolated in composite films. The electrorheological (ER), characteristics of the PANI/SiO₂ composites were investigated. A volume fraction series (φ = 5–25 %) of the PANI/SiO₂/silicone oil dispersions were prepared and sedimentation stabilities were determined. An ER activity was observed from the samples, when subjected to external electric field strength thus, they were classified as smart materials. Some parameters affecting the ER properties of the dispersions such as volume fraction, shear rate, electric field strength, frequency, and temperature were investigated.     

PANI/SnO2导电复合材料的制备及光催化吸附性能

采用水热合成法制备了类球状二氧化锡纳米粉体,再经原位聚合工艺制备聚苯胺(PANI)/SnO2纳米复合材料。利用红外光谱(IR)、X射线衍射(XRD)、扫描电镜(SEM)和透射电镜(TEM)表征了材料的结构和形貌,用四探针测试了材料的电导率,考察了反应物配比对复合材料导电性及光催化吸附性能的影响。结果表明,PANI与SnO2之间存在着化学键的结合,形成交联的孔状结构。复合材料兼具良好的导电性和较高的光催化吸附性能,掺杂30%SnO2纳米粒子时,复合材料的电导率为3.57 S/cm,相比于掺杂态聚苯胺提高了将近十倍,对萘酚绿B的吸附降解率达98%,且循环使用率较高(80%±6%)。     

Synthesis and characterization of polyaniline/activated carbon composites and preparation of conductive films

Polyaniline was synthesized via polyaniline/activated carbon (PANI/AC) composites by in situ polymerization and ex situ solution mixing. PANI and PANI/AC composite films were prepared by drop-by-drop and spin coating methods. The electrical conductivities of HCl doped PANI film and PANI/AC composite films were measured according to the standard four-point-probe technique. The composite films exhibited an increase in electrical conductivity over neat PANI. PANI and PANI/AC composites were investigated by spectroscopic methods including UV–vis, FTIR and photoluminescence. UV–vis and FTIR studies showed that AC particles affect the quinoid units along the polymer backbone and indicate strong interactions between AC particles and quinoidal sites of PANI. The photoluminescence properties of PANI and PANI/AC composites were studied and the photoluminescence intensity of PANI/AC composites was higher than that of neat PANI. The increase of conductivity of PANI/AC composites may be partially due to the doping or impurity effect of AC, where the AC competes with chloride ions. The amount of weight loss and the thermostability of PANI and PANI/AC composites were determined from thermogravimetric analysis. The morphology of particles and films were examined by a scanning electron microscope (SEM). SEM measurements indicated that the AC particles were well dispersed and isolated in composite films.     

Structural,Electrical and Dielectric Properties of Hexa-ferrite-Polyaniline Nano-composites

Ferrite-polyaniline (PANI) composites were prepared by in situ polymerization of polyaniline with the general formula (1 ? x) ferrite + (x) PANI where x = 0, 0.25, 0.5, 0.75, 1. The samples were characterized by XRD, SEM, electrical resistivity, and dielectric measurements. X-ray diffraction reveals single phase formation of CaBaCo₂Al_0.5Fe_11.5O₂₂ Y-type ferrite, whereas polyaniline exhibits an amorphous nature. At room temperature, the resistivity of nano-composites increases with the increase of ferrite filler contents from 3.17 × 10⁴ to 3.19 × 10⁷ Ω cm. Real and imaginary parts of the complex permittivity of the PANI-ferrite composites follow the Maxwell-Wagner model. Based on the Jonscher Law, the AC conductivity of PANI-ferrite composites experiences an increase with the increase in frequency. The exponent calculated from AC conductivity reveals that the hopping is the likely conduction mechanism. The activation energy obtained from temperature-dependent measurements is consistent with room temperature resistivity. Due to the light weight, low cost and flexibility of design, the ferrite-polymer composites are considered useful for microwave devices.     

Study on the infrared property of polyaniline/multi-wall carbon nanotube composite

Composites of polyaniline (PANI) and multi-wall carbon nanotube (MWNT) were synthesized by in situ polymerization with different MWNT content. The composites were characterized by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The SEM photos indicated that a mass of MWNT was enchased into PANI matrix when the content of MWNT was low. With the MWNT content increases, the surface of MWNT was covered with PANI and formed the core-shell structure. From the FT-IR spectroscopy of the composites, it can be confirmed that there was interaction between PANI and multi-wall carbon nanotube. The composites had better thermal stability than pure PANI. Infrared emission property of the composites was analyzed by an IR-II infrared emissivity instrument and an infrared camera. It was found that infrared emission of the composites was lower than pure PANI in all wavelength range and infrared emissivity value was related to the content of MWNT in the composites.     

Enhanced photoactivities of ternary composite coating by antireflection and double P–N heterojunctions

In this paper, we present a convenient and universal strategy to sequentially assemble titania (TiO₂) nanorods and polyaniline (PANI) nanoparticles on the Si wafers through hydrothermal synthesis and chemical oxidation. On the one hand, the composite coatings (PANI/TiO₂/Si) with hierarchical structures reduced the reflectivity to less than 5 % at the wavelengths from 200 to 2500 nm, namely increasing the absorption efficiency of incident light. On the other hand, the double P–N heterojunctions that the composite coatings developed could suppress the recombination of photogenerated carriers, namely enhancing utilization efficiency of absorbed light. The photocurrent density of PANI/TiO₂/Si was above two times higher than that of TiO₂/Si at 1.5 V of positive potentials. The application of such coatings in the photocatalysis area, which are fabricated with this method, is thus straightforward.