Preparation and electroactivity of polyaniline/poly(acrylic acid) film electrodes modified by platinum microparticles

The preparation and properties of poly(acrylic acid) (PAA)-doped polyaniline (PANI) film electrodes further modified by electrodeposition of platinum particles were investigated by cyclic voltammetry and in situ conductivity measurement. The PANI/PAA film exhibits a better electroactivity and higher stability, even in solutions of lower acidity, although its polymerization rate is decreased three-fold compared to that of PANI. The conductivity of the PANI/PAA film increases by a factor of two compared to that of PANI. The effects of the carboxylic acid groups of PAA in the PANI matrix on the performance of the film are discussed. The electrocatalytic activity of PANI/PAA/Pt for reduction of hydrogen and oxidation of MeOH is higher than that of PANI modified with Pt particles alone. Characterization of the electrodes by SEM shows the platinum modification procedure yields roughly spherical catalyst particles 0.51mum in diameter dispersed throughout the polyaniline.     

Processable conductive blends of polyaniline/polyimide

By using camphorsulfonic acid (CSA) to protonate polyaniline (PANI), the counterion enabled the PANI–CSA complex processable as a solution phase. So camphorsulfonic acid (CSA)-doped polyaniline/polyimide (PANI/PI) blend films were prepared by the solvent casting method using N-methylpyrrolidinone (NMP) as a cosolvent followed by thermal imidization. The conductivity of the PANI–CSA/PAA (50 wt % PANI content) is greater than that of the pure PANI sample at room temperature. As the thermal imidization proceeded, molecular order of polymer chain structure was improved in the resulting PANI–CSA/PI film due to the annealing effect of PANI chain, and this PANI–CSA/PI film showed higher conductivity than PANI–CSA and PANI–CSA/PAA film. PANI–CSA/PI blend films had a good thermal stability of conductivity at high temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1863–1870, 1998     

铂微粒修饰聚苯胺膜电极对甲酸电催化氧化的研究

采用循环伏安法研究Pt盘电极 (Pt)、铂微粒修饰Pt盘电极 [Pt(Pt) ]和Pt微粒修饰聚苯胺膜电极 [PAN(Pt) ]对甲酸电催化氧化行为的影响 ,比较了它们对甲酸电催化氧化的活性 ,发现PAN(Pt)电极对甲酸电催化氧化的表观电流密度为 3 79× 10 2 mA·cm-2 ,分别比Pt、Pt(Pt)和Pt-PDMA/Pt电极约高 2 35、2 5和 6 3倍。峰电位比Pt PDMA/Pt电极约低 0 16V。     

Chemical and electrochemical synthesis of polyaniline/platinum composites

The synthesis of polyaniline/platinum composites (PANI/Pt) has been achieved using both chemical and electrochemical methods. The direct chemical synthesis of PANI/Pt proceeds through the oxidation of aniline by PtCl₆²⁻ in the absence of a secondary oxidant. SEM images of these samples indicate that the Pt particles are on the order of ∼1 μm for the chemically prepared composite. Electrochemical PANI/Pt synthesis is initiated by the uptake and reduction of PtCl₆²⁻ into an a priori electrochemically deposited PANI film. This method produces a uniform dispersion of Pt particles with smaller particles with diameters ranging between 200 nm and 1 μm. The results indicate that electrochemical methods may be more suitable for controlling particle dimension. Both materials show reduced proton doping relative to PANI without Pt, indicating the metal particles directly influence proton doping and the oxidation state of the polymer. The electrochemical data indicate that the conductivity in solution is sufficient such that the normal acid doping is attainable for PANI/Pt produced using either synthetic method.     

Electrocatalytic oxidation of methanol and C1 molecules on highly dispersed electrodes Part II: Platinum-ruthenium in polyaniline

The oxidation of methanol and C1 molecules at electrodes modified with polyaniline and particles of platinum and ruthenium has been studied in aqueous HClO₄ electrolyte. The platinum and ruthenium particles were incorporated into the polyaniline film by electrochemical reduction. The activity for the oxidation of C1 molecules is higher for bimetallic electrodes than for polyaniline-coated electrodes modified with platinum alone. Indeed, a negative shift of more than 100 mV is observed as compared to the potential obtained with a polyaniline film modified by pure platinum. Moreover, the oxidation of methanol is faster and more complete on the Pt-Ru modified polyaniline electrode, since carbon dioxide is the main reaction product.     

Electrochemical polymerization of aniline in the presence of poly(acrylic acid) and characterization of the resulting films

Conducting films composed of polyaniline (PANI) and poly(acrylic acid) (PAA) were prepared by electrochemical polymerization of aniline in the presence of PAA. The PAA content in the films (PANI/PAA films) was controlled by the concentration of PAA in polymerization solution, and the properties of the films were investigated in relation to the PAA content. It was demonstrated by means of scanning electron microscopy and cyclic voltammetry that the surface morphology and electrochemical property of the films were affected significantly by the PAA content. In contrast, the conductivity of the films was found hardly dependent on the PAA content up to 18 wt %. The cyclic voltammetry gave an interesting result that the PANI/PAA films showed an electroactivity in neutral solution, which was not observed for the PANI film without PAA, and the electroactivity was closely related to the PAA content in the PANI/PAA films.     

Polyaniline‐supported platinum‐hydrous ruthenium oxide nanocomposite as electrocatalyst for methanol oxidation

A novel composite electrode is fabricated through the electrodeposition of hydrous ruthenium oxide (RuO₂·xH₂O) and platinum (Pt) particles into the matrix of polyaniline (PANI). Scanning electron microscopy reveals that RuO₂·xH₂O and Pt particles are homogeneously distributed into the matrix of PANI. A comparison of the sizes of Pt and RuO₂·xH₂O particles incorporated into the PANI film reveals that Pt particles are smaller in sizes as compared with the sizes of RuO₂·xH₂O particles. The catalytic activity of composite electrodes was evaluated for the oxidation of methanol by using cyclic voltammetry and chronoamperometry. A relatively high catalytic current was noticed for the oxidation of methanol (2.37 mA/cm²) at PANI‐Pt‐RuO₂·xH₂O electrode (+0.6 V (V vs. Ag/AgCl) in comparison to oxidation current at PAN‐Pt (1.27 mA/cm²) electrode. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Bio- and bioelectro-catalytic properties of polyaniline/poly(acrylic acid) composite films bearing covalently-immobilized acid phosphatase

Conducting films composed of polyaniline (PANI) and poly(acrylic acid) (PAA) were prepared by electrochemical polymerization of aniline in the presence of various concentrations of PAA. The content of PAA moiety on the surface of the composite films (PANI/PAA films) was estimated by determination of carboxyl groups and found to be controlled by the concentration of PAA in polymerization solution. Acid phosphatase (ACP) was immobilized covalently on the PANI/PAA films by the condensation reaction with the carboxyl groups on the films. It was confirmed that the enzyme activity of the ACP-immobilized PANI/PAA film increased with increasing content of PAA moiety on the surface of the film, accompanying an increase in the amount of the immobilized ACP. The activity of the covalently immobilized ACP was significantly higher than that of the ACP adsorbed on the PANI/PAA film. By use of the ACP-immobilized PANI/PAA film as an enzyme electrode, bioelectrocatalytic oxidation of L-ascorbic acid 2-phosphate (ASA2P) was examined. The enzyme electrode gave the current due to the oxidation of ASA2P in proportion to the content of PAA moiety on the surface of the PANI/PAA film used, which was relevant to the activity of the covalently immobilized ACP.     

Polyaniline-carbon composite films as supports of Pt and PtRu particles for methanol electrooxidation

Vulcan XC-72 carbon black particles (average size: ca. 50 nm) was incorporated into polyaniline (PANI) matrix by an electrochemical codeposition technique during the electropolymerization process. The doping by carbon particles leads to a higher polymeric degree and a lower defect density in the PANI structure. Furthermore, the incorporation of carbon particles not only increases the electrochemical accessible surface areas (S_a) and electron conductivity of the PANI film, but also decreases charge transfer resistance at PANI/electrolyte interfaces. Therefore, as expected, a fabricated PANI + C composite film with dispersed Pt and PtRu particles exhibited excellent electrocatalytic activity for methanol oxidation due to better Pt dispersion and utilization. The PANI + C composite film is more promising as a support material in electrocatalysis than a PANI film. Meanwhile, a new application for regular carbon black as a doping material into conducting polymer for electrocatalysis was thus demonstrated.     

Electrically conducting polyaniline–poly(acrylic acid) blends

We report an electrically conducting polyaniline–poly(acrylic acid) blend coatings prepared by mixing the emeraldine base (EB) form of polyaniline (PANI) and poly(acrylic acid) (PAA) aqueous solution. The samples show a moderate electrical conductivity σ. If they are immersed in an HCl aqueous solution, the conductivity of the samples is increased by two or three orders of magnitude and their thermal stability is also improved. Optical transmittance spectra show a complete protonation of PANI–PAA blends after immersion in HCl aqueous solution. Fourier transform infrared spectroscopy studies indicate that the better thermal stability of σ could come from the more stable protonated imine nitrogen ions. A low percolation threshold phenomenon is observed in PANI–PAA blends, from a strong interaction between the carboxylic acid groups of PAA and the nitrogen atoms of PANI. © 1998 SCI.     

Polythiophene, polyaniline and polypyrrole electrodes modified by electrodeposition of Pt and Pt+Pb for formic acid electrooxidation

The electrosynthesis of polythiophene (PTh), polyaniline (PANI) and polypyrrole (PPy) films modified by dispersion of Pt or Pt+Pb and its employment in the electrocatalytic oxidation of HCOOH are studied and compared. The influence of parameters such as polymer film thickness, the number of dispersed Pt particles, the amount of Pb deposited and the presence of Pb2+ in the electrolyte on the electrooxidation of HCOOH is investigated. Electrode systems including the polymer and a mixture of Pt and Pb particles show a better electrocatalytic activity than electrodes having a polymer–Pt combination or bulk Pt electrodes. Furthermore, during the electrooxidation of HCOOH using polymer–(Pt+Pb) electrodes the presence of fewer poisoning species is observed, indicating that the role of Pb in these electrode systems is in agreement with the Pb adatom effect observed when bulk Pt electrodes are used. However, the presence of Pb(ii) in the electrolyte is not required for the PTh–(Pt+Pb) electrode system and, in addition, a better electrocatalytic effect is obtained in this case. With application of an appropriate E/t program the activity is unchanged over a long time.     

Oxidative graft polymerization of aniline on the modified surface of polypropylene films

A novel method for preparing electrically conductive polypropylene‐graft‐polyacrylic acid/polyaniline (PP‐g‐PAA/PANI) composite films was developed. 1,4‐Phenylenediamine (PDA) was introduced on the surface of PP‐g‐PAA film, and then, chemical oxidative polymerization of aniline on PP‐g‐PAA/PDA film was carried out to prepare PP‐g‐PAA/PANI electrically conductive composite films. After each step of reaction, the PP film surface was characterized by attenuated total reflectance Fourier transform infrared spectroscopy. Static water contact angles of the PP, PP‐g‐PAA, and PP‐g‐PAA/PANI films were measured, and the results revealed that graft reactions took place as expected. The morphology of the PP‐g‐PAA film and the PP‐g‐PAA/PANI composite film were observed by atomic force microscopy. The conductivity and the thickness of the PP‐g‐PAA/PANI composite films with 1.5 wt % PANI were around 0.21 S/cm and 0.4 μm, respectively. The PANI on the PP‐g‐PAA/PANI film was reactivated and chain growing occurred to further improve the molecular weight of PANI. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2442–2450, 2007     

载铂聚苯胺/聚砜复合膜修饰电极对甲醇的电催化氧化行为研究

采用循环伏安法制备聚苯胺(PAN)/聚砜(PSF)复合膜修饰电极,在其上电沉积铂粒子,制得载铂聚苯胺/聚砜复合膜修饰电极,用循环伏安法和交流阻抗法研究它对甲醇的电催化氧化行为。复合膜的化学组分用FTIR进行表征,复合膜内层载铂后的表面形态用SEM进行表征。结果表明,复合膜的内层(与工作电极接触的一面)是聚苯胺,外层(与溶液接触的一面)是聚砜,铂粒子在复合膜内层的多孔聚苯胺上均匀沉积,从而使载铂聚苯胺/聚砜复合膜修饰电极对甲醇有好的电催化氧化性能。     

Effects of conductive polyaniline (PANI) preparation and platinum electrodeposition on electroactivity of methanol oxidation

A modified galvanostatic method, termed the ‘pulse galvanostatic method’ (PGM) was used to synthesize nanofibular polyaniline (PANI). In contrast to granular PANI prepared by the conventional galvanostatic method (GM), nanofibular PANI has better conductivity and higher specific surface area. The nanofibular PANI electrode modified by Pt microparticles, at the same Pt loading, exhibits a considerably higher electrocatalytic activity on the methanol oxidation than that of the granular PANI electrode modified by Pt microparticles. Furthermore, the PGM method can be used as a good method for Pt microparticle electrodeposition. The composite electrode composed of PANI and Pt microparticles has the best electrocatalytic activity in the experimental range. The effects of Pt loading and methanol concentration, on the electrocatalytic activity for methanol oxidation have also been researched.     

Synthesis of high conductivity Polyaniline/Ag/graphite nanosheet composites via ultrasonic technique

A new process for the synthesis of high conductivity polyaniline/Ag/graphite nanosheet (PANI/Ag/NanoG) composites was developed. Graphite nanosheet was prepared by treating the expanded graphite in aqueous alcohol solution using sonication, and a uniform silver film about 470 nm thick was obtained on graphite nanosheet surface via an improved electroless plating method. Then PANI/Ag/NanoG composites were fabricated via in situ polymerization of aniline monomer in the presence of silver coated graphite nanosheet through using ultrasonic technique. The sliver particles and composites were evidenced by scanning and transmission electron microscopy examinations, the results showed that the silver coated graphite nanosheet particles played an important role in forming conducting bridge in polyaniline matrix. According to the electrically test, the conductivity of the PANI/Ag/NanoG composites was dramatically increased compared with pure PANI. From the thermogravimetric analysis, the PANI/Ag/NanoG composites exhibited a beneficial effect on the thermal stability of pure PANI.     

Electrical and structural analysis of conductive polyaniline/polyimide blends

Conducting films of dodecylbenzenesulfonic (DBSA)‐doped polyaniline/polyimide (PANI/PI) blends with various compositions were prepared by solvent casting followed by a thermal imidization process. Electrical and physical properties of the blends were characterized by infrared spectroscopy, an X‐ray diffraction technique, thermal analysis, a UV‐vis spectrophotometer, a dielectrometer, and conductivity measurements. The blends exhibited a relatively low percolation threshold of electrical conductivity at 5 wt % PANI content and showed higher conductivity than that of pure DBSA‐doped PANI when the PANI content exceeded 20 wt %. A lower percolation threshold and a lower compatibility was shown between the two components in the blends than those of PANI–camphorsulfonic acid/polyamic acid (PANI–CSA/PAA). A well‐defined layered structure due to the alignment of the long alkyl chain dopant perpendicular to the PANI main chain was evidenced by WAXD spectra. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2169–2178, 1999     

Analysis of high-frequency distortions in impedance spectra of conducting polyaniline film modified Pt-electrode measured with different cell configurations

Distortions of high-frequency parts of impedance spectra of conducting polyaniline, PANI, film modified Pt electrodes in 0.5 and 0.05 mol dm⁻³ H₂SO₄ are analysed in terms of overlapping between impedance of PANI film working electrode (WE) branch and artefact impedance(s) induced by measurements in two-electrode (symmetrical, PANI versus PANI and asymmetrical, PANI versus platinised Pt) and three-electrode (with conventional reference (RE) and pseudo-reference (PRE) electrode) cells. In impedance measurements with both two-electrode cell configurations and PANI film WE at equilibrium, high-frequency distortions are generated by contribution of inductive impedance originating from instruments and wirings. Extent of distortions is found inversely proportional to the solution resistance term. In impedance measurements with conventional three-electrode cell configuration and PANI film WE kept at polarized conditions, relatively high extent of high-frequency distortions is generated by couplings between three electrodes of similar impedances. Distortions are manifested as inductive/capacitive artefact impedance, with lower inductivity and higher capacity for lower solution resistance and vice versa. Low impedance PRE is found useful for simultaneous diminishing of inductive and capacitive artefact impedances, what in some conditions could result with impedance spectra showing minor high-frequency distortions. Use of proper transfer function(s) with impedance of experimental artefacts involved, is in all cases found essential not only for determination of all parameters characterizing fast impedance response of PANI film WE, but for highlighting physical origins and possible ways of control of the content of experimental artefacts in measured impedance spectra too.     

Oxidation of hydrogen at platinum-polypyrrole electrodes

Polypyrrole, an electronic conducting polymer, is used as a matrix for the dispersion of Pt particles. These particles can be included by two methods, viz. (1) by electrochemical depositin of platinum particles on a polypyrrole covered glassy carbon disc and (2) by incorporation of Pt particles during the polymerization of pyrrole on a glassy carbon disc. As a model reaction the oxidation of hydrogen at these electrodes is studied. The polypyrrole electrodes prepared by method (1) exhibit a good catalytic behaviour. The other type of electrodes however show, despite the higher Pt loading, much less activity. Additionally, electrodes were prepared according to method (1) with poly(N-methylpyrrole) and polyaniline as the conducting polymer. These electrodes show a similar diffusion limited behaviour for the oxidation of hydrogen as polypyrrole-modified electrodes, however the oxidation starts at a much higher potential.     

Electrooxidation of β-D(+)glucose on bare and u.p.d. modified platinum particles dispersed in polyaniline

Platinum particles dispersed in a polyaniline film (PAni/Pt) provide a better catalyst than smooth Pt for the electrooxidation of -d(+)glucose in perchloric acid aqueous solutions. The Pt particles are less sensitive to poison formation than smooth platinum. Their catalytic activity is influenced by modification with underpotential deposition (u.p.d.) of thallium, lead or bismuth. Up to 0.4V vs RHE the Pt particles show a better activity than u.p.d.- modified platinum particles. However, above 0.4V the u.p.d.-modified particles are more active than bare Pt particles. Underpotential deposition of cadmium inhibits the electrooxidation of - d(+)glucose. The morphology and the nature of the metallic dispersion were examined by transmission electron microscopy.     

Electrocatalytic oxidation of methanol on Cu modified polyaniline electrode in alkaline medium

Electrolytically deposited Cu on polyaniline film covered Pt substrate (Cu/PANI/Pt) is used as anode for the electrooxidation of methanol in alkaline medium. The electrochemical behavior and electrocatalytic activity of the electrode were characterized using cyclic voltammetry, impedance spectroscopy, chronomethods, rotating disc voltammetry and polarization studies. The morphology and composition of the modified film were obtained using SEM and EDAX techniques. The electrooxidation of methanol in NaOH is found to be more efficient on Cu/PANI/Pt than on bare Cu (Cu), electrodeposited Cu on Cu (Cu/Cu) and electrodeposited Cu on Pt (Cu/Pt) substrates. Partial chemical displacement of dispersed Cu on PANI with Pt or Pd further improved its performance towards methanol oxidation.