The study on the application of solid-state method for synthesizing the polyaniline/noble metal (Au or Pt) hybrid materials

The solid-state method was applied for synthesizing polyaniline (PANI)/noble metal hybrid materials with the presence of HAuCl₄·4H₂O or H₂PtCl₆·6H₂O in the reaction medium. The structure, morphology, and electrochemical activity of the composites were characterized by Fourier transform infrared (FTIR) spectra, UV-visible (vis) absorption spectra, energy dispersive spectrum (EDS), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and cyclic voltammetry. The results from FTIR and UV-vis spectra showed that the oxidation degree and doping level of the PANI in composites can be influenced by HAuCl₄·4H₂O and H₂PtCl₆·6H₂O. The EDS data demonstrated that the composites contain a certain amount of Au (or Pt) element. XRD analysis indicated the presence of crystalline-state Au particles in PANI matrix prepared from the presence of HAuCl₄·4H₂O and revealed that the H₂PtCl₆·6H₂O cannot be converted into metal Pt. The TEM and SEM images implied that the Au particles did exist in the polymer matrix with the size of about 20 nm. The enzymeless H₂O₂ sensor constructed with PANI/Au composite from the presence of HAuCl₄·4H₂O showed a short response time (within 5 s) and displayed an excellent performance in wide linear range.     

Conducting polyaniline composite: From syntheses in waterborne systems to chemical sensor devices

The development of a conducting composite from its one-step synthesis in aqueous dispersed medium to the characterization of its chemical sensor performance is detailed. Composite films of polyaniline and polyacrylate were processed from the crude dispersion with no need for post-formulation. The synthesis has been optimized to be as simple, cheap and transferable as possible. The composite composition is tunable, i.e. the nature of the dopant was varied and its effect on kinetic parameters was observed. Ab initio calculations have been performed on a series of six ionic systems to gain a deeper insight into the contribution of both the stability of the anilinium salts in the composite polymerization. The conductivities of all composites were recorded from room temperature to 150 °C and the thermal stability versus dopant highlighted. The conducting films were then studied as active layers in a chemical sensor. The results showed that these composites, easily synthesized and processed, are ammonia sensitive and exhibit a fast response when exposed to air pollution.     

Polyaniline and polypyrrole prepared in the presence of surfactants: a comparative conductivity study

Polyaniline and polypyrrole have been prepared by chemical oxidative polymerization of the corresponding monomers in an aqueous medium containing an anionic surfactant—sodium bis(2-ethylhexyl) sulfosuccinate, dodecylbenzenesulfonic acid and its sodium salt, and sodium dodecyl sulfate. Determination of the yield, elemental composition and density proved, and FTIR spectroscopy confirmed, that the anionic surfactants become incorporated in the conducting polymers. The polymerizations in the presence of a cationic surfactant, tetradecyltrimethylammonium bromide, were carried out for comparison. While the conductivity of polypyrrole became enhanced after the introduction of an anionic surfactant, the changes in the conductivity of polyaniline were marginal. The conductivity changes in both polymers during thermal ageing were measured at 175 °C. The electrical stability of polyaniline was better than that of polypyrrole. The presence of a surfactant improved the stability of conductivity of polypyrrole but reduced the electrical stability of polyaniline.     

On the molecular properties of polyaniline: A comprehensive theoretical study

A comprehensive study about the molecular and electronic properties of the different forms of polyaniline has been developed using quantum mechanical calculations. Initially the performance of different ab initio and DFT quantum mechanical methods has been evaluated by comparing the results provided for small model compounds containing two repeating units. After this, calculations on the emeraldine base, leucoemeraldine base, pernigraniline base and emeraldine salt (monocationic and dicationic) forms of oligoanilines with n repeating units, where n ranged from 5 to 13, have been performed using the BH&H/6-31G(d) method, which was found to be a very suitable theoretical procedure. Interestingly, calculations indicate that the distribution in blocks of the repeating units containing amine and imine nitrogen is largely preferred for the emeraldine base form. On the other hand, the molecular structure and band gap of the emeraldine base, leucoemeraldine base and pernigraniline base forms have been rationalized according to their differences in the conjugation of the C₆H₄ rings. Calculations on cationic oligoanilines indicate that, when the emeraldine salt form presents a doublet electronic state, the positive charge and the spin density are located in the middle of the chain extending through five consecutive repeating units.     

Polyaniline-silver composites prepared by the oxidation of aniline with mixed oxidants, silver nitrate and ammonium peroxydisulfate: The control of silver content

Aniline was oxidized with mixtures of two oxidants, ammonium peroxydisulfate and silver nitrate, to give polyaniline-silver composites with variable content of silver in the composites. The presence of peroxydisulfate has a marked accelerating effect on the oxidation of aniline with silver nitrate. Oxidations in 1 M methanesulfonic acid produced composites in high yield. The molecular structure of the polyaniline was confirmed by UV-visible and FTIR spectra, and the polymeric character was established by gel-permeation chromatography. The content of silver varied between 0 and 70 wt.%. The silver nanoparticles were smaller than 100 nm. The conductivity of the composites was of the order of units S cm⁻¹. Only at high silver nitrate contents in the reaction mixture, the conductivity of products exceeded 100 S cm⁻¹. The conductivity of the composites sometimes increased after deprotonation of the polyaniline salt to a non-conducting base. Such conductivity behaviour is discussed in terms of the percolation model.     

In situ investigation of corrosion localised at the buried interface between metal and conducting polymer based composite coatings

Conducting polymers are controversially discussed for application in corrosion protection. In our earlier work we presented a hypothesis for explaining why sometimes very good performance is observed and sometimes fast and disastrous coating break-down, especially in the presence of defects in the coating. By avoiding continuous macroscopic networks of conducting polymer in composite coatings the latter can be prevented, opening up the application of conducting polymers for secure performance in intelligent corrosion protection. In this paper we add further proof. However, at the interface between coating and metal, corrosion induced by galvanic coupling between conducting polymer and the metal still remains a problem, even in the absence of defects in the coating. Now we found that for some metals this corrosion at the buried interface can be studied in situ by Scanning Kelvin Probe microscopy, providing the means to better develop strategies for counter acting this problem.     

Preparation and corrosion resistance of nanostructured PVC/ZnO–polyaniline hybrid coating

ZnO–polyaniline nanocomposite with core–shell nanostructure was prepared by in situ polymerization of aniline monomer in the presence of ZnO nanoparticles. Fourier transform infrared spectroscopy, X-ray diffraction patterns, field emission scanning electron microscopy and transmission electron microscopy techniques were used to characterize the composition and structure of ZnO–polyaniline nanocomposite. d.c. electrical conductivity measurement showed that the electrical conductivity of ZnO–polyaniline nanocomposite pellets is higher than that of pristine polyaniline and ZnO nanoparticles pellets. The addition of ZnO nanoparticles causes to the increasing of polyaniline electrical conductivity. ZnO–polyaniline nanocomposite was mixed with polyvinyl chloride (PVC) through a solution mixing method and the three components PVC/ZnO–polyaniline hybrid material was applied as coating on iron coupon by the solution casting method. Corrosion protection efficiency of PVC/ZnO–polyaniline hybrid coating on iron coupons was studied by open circuit potential and Tafel techniques in 3.5% NaCl solution as corrosive environment. According to the results, PVC/ZnO–polyaniline hybrid nanocomposite coating showed dramatically increased corrosion protection effect on iron samples compared to that of uncoated iron coupon and pure polyaniline anticorrosive coating. It was found that ZnO nanoparticles improve the barrier and electrochemical anticorrosive properties of polyaniline and the addition of polyvinyl chloride increases the barrier effect of polyaniline coating.     

Synthesis and Characterization of a Conducting Composite of Polyaniline,Poly(o-Anisidine), and Poly(Aniline-co-o-Anisidine)

A conducting composite of polyaniline, poly(o-anisidine), and poly(aniline-co-o-anisidine) using incorporation of TiO₂ and SiO₂ was prepared by electrochemical polymerization. The films were electropolymerized in a solution containing 0.1 M monomer(s), 1 M sulfuric acid as supporting electrolyte, and 10^?5 M TiO₂ and SiO₂ by applying a sequential linear potential scan rate of 50 mV/s between ? 0.2 and 1.0 V versus an Ag/AgCl electrode. The composites were characterized by cyclic voltametry, UV-visible spectroscopy, electrical conductivity, and thermogravimetric analysis. It was observed that the UV-visible peaks appeared in the region of the conducting emerladine salt phase. In an overall study, the polymers prepared using TiO₂ had a higher conductivity than those prepared with SiO₂; however, higher conductivity was observed for the polyaniline-TiO₂ conducting composite than for the other polymers. The composites did not lose their color at higher temperature and hence can be utilized as the conductive pigments required for antielectrostatic applications.     

Trends in Conducting Polymer and Hybrids of Conducting Polymer/Carbon Nanotube: A Review

Several conducting polymers, including polyaniline, polypyrrole, polythiophene, polyvinylpyrrolidone, poly(3,4-ethylenedioxythiophene), poly(m-phenylenediamine), polynaphthylamine, poly(p-phenylene sulfide), and their carbon nanotube reinforced nanocomposites are discussed in this review. The physical, electrical, structural and thermal properties of polymers along with synthesis methods are discussed. A concise note on carbon nanotubes regarding their purification, functionalization, properties and production are reported. Moreover, the article focuses upon synthesis methods, properties and applications of conducting polymer/carbon nanotube nanocomposites are focused. Nanotube dispersion, loading concentration and alignment within conducting polymer/carbon nanotube nanocomposite affect their performance and morphology. The conducting polymer/carbon nanotube nanocomposites are substantially used in sensors, energy storage devices, supercapacitors, solar cells, EMI materials, diodes, and coatings.     

Synthesis and Characterization of Metal Nanoparticle Embedded Conducting Polymer–Polyoxometalate Composites

Phosphomolybdate has been employed simultaneously as the oxidizing agent for the monomer polymerization and the reduced polyoxometalate is used as reducing agent for the reduction of metal ions. The composites thus obtained have been characterized and may have many potential applications.     

Electrochemical Synthesis and Characterization of Conducting Copolymer: Poly(o-aniline-co-o-anisidine)

Copolymerization of o-anisidine and o-anisidine was achieved electrochemically in aqueous solution containing H₂SO₄ as supporting electrolyte. The copolymer compositions can be altered by varying the monomer feed ratios during electrosynthesis. The films were electropolymerized in solution containing monomers in various ratio (0.025–0.1 M) and 1 M sulphuric acid as electrolyte by applying sequential linear potential scan rate 50 mV/s between ? 0.2 to 1.0 V. versus Ag/AgCl electrode. The copolymers were characterized by cyclic voltammetric, conductivity measurement, UV-Visible spectroscopy, FT-IR spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and CHN elemental analysis.     

Marine paint fomulations: Conducting polymers as anticorrosive additives

Within coating technology, there is increasing interest in the development of efficient anticorrosive additives able to replace the conventional inorganic anticorrosive pigments usually added to paints, which may have detrimental effects on both environment and health. A number of recent studies have evidenced that the modification of a paint formulation by the addition of a low concentration of conducting polymer (0.2–0.3%, w/w) increases significantly the protective properties of the coating. Here we focus on the principles of anticorrosive additives based on conducting polymers for marine paints. The article reviews the most important findings achieved in recent studies. The relevant factors that are determinant for the anticorrosive protection imparted by conducting polymers, as the doping level, the miscibility with paint, the electrochemical stability, etc., are discussed in detail.     

新型镍/硅藻土磁性纳米粒子催化剂的合成及应用

合成了一种新型镍/硅藻土磁性纳米粒子催化剂,并将其应用于硝基还原反应。通过X射线衍射、透射电子显微镜和扫描电子显微镜等手段对催化剂进行了表征。X射线衍射结果表明,金属镍、氧化镍与二氧化硅载体共存。透射电镜照片显示催化剂主要是非晶相,部分团聚,存在大量镍和氧化镍的分散小颗粒。扫描电镜图像显示催化剂颗粒具有良好的分散性,颗粒大小（30~70） nm。催化剂的主要优点是在低于423 K的空气中可以稳定存在,加氢使用前不用活化。在催化剂性能考察中,反应效果好,产物收率高;催化剂通过简单的磁分离可以进行回收再利用。     

Ferrocenium hexafluorophosphate-induced nanofibrillarity of polyaniline-polyvinyl sulfonate electropolymer and application in an amperometric enzyme biosensor

The formation of nanofibrillar polyaniline-polyvinyl sulfonate (Pani-PVS) composite by electropolymerization of aniline in the presence of ferrocenium hexafluorophophate (FcPF₆) and its application in mediated-enzyme biosensor using the horseradish peroxidase/hydrogen peroxide (HRP/H₂O₂) enzyme-substrate system is reported. The electropolymerization was carried out at glassy carbon electrodes (GCE) and screen printed carbon electrodes (SPCE) in a strongly acidic medium (HCl). Scanning electron microscopy (SEM) images showed that 100 nm diameter nanofibrils were formed on the SPCE in contrast to the 800-1000 nm cauliflower-shaped clusters which were formed in the absence of FcPF₆. A model biosensor (GCE//Pani-PVS/BSA/HRP/Glu), consisting of horseradish peroxidase (HRP) immobilized by drop coating atop the GCE//Pani-PVS in the presence of bovine serum albumin (BSA) and glutaraldehyde (glu) in the enzyme layer casting solution, exhibited voltammetric responses characteristic of a mediated-enzyme system. The biosensor response to H₂O₂ was very fast (5 s) and it exhibited a detection limit of 30 μM (3σ) and a linearity of up to 2 mM (R² = 0.998). The relatively high apparent Michaelis-Menten constant value () of the sensor indicated that the immobilized enzyme was in a biocompatible microenvironment. The freshly prepared biosensor was successfully applied in the determination of the H₂O₂ content of a commercial tooth whitening gel with a very good recovery rate (97%).     

Protein functionalized Pt nanoparticles-conducting polymer nanocomposite film: Characterization and immunosensor application

We report an electrochemically prepared 3-mercaptopropionic acid (MPA) capped Pt nanoparticles-Polypyrrole (PPy) nanocomposite film based bioelectrode for the detection of human C-reactive protein (αCRP). The electrochemical deposition provides homogeneous distribution of ultrafine Pt(MPA)-NPs within the uniform and adherent PPy film with high degree of geometrical conformity and controllable film thickness. Protein antibody, Ab-αCRP, was covalently immobilized through the site specific carboxyl groups of Pt(MPA)-NPs within the polymer nanocomposite film by carbodiimide coupling reaction. The bioelectrode interfacial surface electron transport study towards protein antigen, Ag-αCRP, was carried out by electrochemical impedance spectroscopy (EIS). The value of ‘n’, a Constant Phase Element exponent used as a gauge of the heterogeneity, for Pt(MPA)-PPy nanocomposite film was found to be 0.88∼1 which is indicative of a homogeneous morphology of the composite film with minimal defects. The EIS of the bioelectrode exhibited significant changes in charge transfer resistance (R_et) component at a low ac frequency of <20 Hz towards Ag-αCRP detection over a linear range of 10 ng mL⁻¹–10 μg mL⁻¹ in PBS with a sensitivity of 109.74 Ωcm² per decade.     

Gold microspheres with hierarchical structure/conducting polymer composite film: Preparation, characterization and application as catalyst

Monodisperse gold microspheres with novel hierarchical structure and their composite integrated with a conducting film obtained from a new conducting copolymer, poly(acrylonitrile-co-vinyl acetate) -graft- poly(3,4-ethylenedioxythiophene), have been successfully prepared in one step via the in-situ reduction of AuCl₄^- on the conducting film surface. The morphology and structure of the as-prepared composite film are characterized, and its catalytic effect on reduction of p-nitrophenol is investigated. By controlling the concentration of HAuCl₄ and the conductivity (or PEDOT content) of P(AN-co-VA)-g-PEDOT copolymer film, the amount and the size of gold microspheres can be effectively adjusted. It is suggested that the side poly(3,4-ethylenedioxythiophene) chains of the conducting copolymer play both reducing and structure-directing roles during the formation of Au microspheres with hierarchical structure.     

油溶性纳米MoS2加氢催化剂的合成、表征和应用

传统MoS₂加氢催化剂粒径大、油溶性差而催化效率相对较低。纳米粒子合成方法很多，其中液相化学合成技术尤其水(溶剂)热、微乳液、单层二硫化钼重堆积和微波液相介电加热法等更为便捷、高效。在油溶性纳米MoS₂的合成中，表面修饰剂的选择最为关键。综述了油溶性纳米MoS₂的合成、表征和应用研究进展，提出了高稳定性、高活性和油溶性纳米MoS₂加氢催化剂高效合成优化参数，为实现工业应用提供了参考。     

Effect of nanoparticle loading and magnetic field application on the thermodynamic,optical, and rheological behavior of thermoresponsive polymer solutions

Although processing via external stimuli is a promising technique to tune the structure and properties of polymeric materials, the impact of magnetic fields on phase transitions in thermoresponsive polymer solutions is not well-understood. As nanoparticle (NP) addition is also known to impact these thermodynamic and optical properties, synergistic effects from combining magnetic fields with NP incorporation provide a novel route for tuning material properties. Here, the thermodynamic, optical, and rheological properties of aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions are examined in the presence of hydrophilic silica NPs and magnetic fields, individually and jointly, via Fourier-transform infrared spectroscopy (FTIR), magneto-turbidimetry, differential scanning calorimetry (DSC), and magneto-rheology. While NPs and magnetic fields both reduce the phase separation energy barrier and lower optical transition temperatures by altering hydrogen bonding (H-bonding), infrared spectra demonstrate that the mechanism by which these changes occur is distinct. Magnetic fields primarily alter solvent polarization while NPs provide PNIPAM–NP H-bonding sites. Combining NP addition with field application uniquely alters the solution environment and results in field-dependent rheological behavior that is unseen in polymer-only solutions. These investigations provide fundamental understanding on the interplay of magnetic fields and NP addition on PNIPAM thermoresponsivity which can be harnessed for increasingly complex stimuli-responsive materials.     

State of arts on the bio-synthesis of noble metal nanoparticles and their biological application

Nanomaterials are materials in which at least one of the dimensions of the particles is 100 nm and below. There are many types of nanomaterials, but noble metal nanoparticles are of interest due to their uniquely large surface-to-volume ratio, high surface area, optical and electronic properties, high stability, easy synthesis, and tunable surface functionalization. More importantly, noble metal nanoparticles are known to have excellent compatibility with bio-materials, which is why they are widely used in biological applications. The synthesis method of noble metal nanoparticles conventionally involves the reduction of the noble metal salt precursor by toxic reaction agents such as NaBH₄, hydrazine, and formaldehyde. This is a major drawback for researchers involved in biological application researches. Hence, the bio-synthesis of noble metal nanoparticles (NPs) by bio-materials via bio-reduction provides an alternative method to synthesize noble metal nanoparticles which are potentially non-toxic and safer for biological application. In this review, the bio-synthesis of noble metal nanoparticle including gold nanoparticle (AuNPs), silver nanoparticle (AgNPs), platinum nanoparticle (PtNPs), and palladium nanoparticle (PdNPs) are first discussed. This is followed by a discussion of these biosynthesized noble metal in biological applications including antimicrobial, wound healing, anticancer drug, and bioimaging. Based on these, it can be concluded that the study on bio-synthesized noble metal nanoparticles will expand further involving bio-reduction by unexplored bio-materials. However, many questions remain on the feasibility of bio-synthesized noble metal nanoparticles to replace existing methods on various biological applications. Nevertheless, the current development of the biological application by bio-synthesized noble metal NPs is still intensively ongoing, and will eventually reach the goal of full commercialization.