Gas Sensing Ability of a Nanostructured Conducting Polypyrrole Film Prepared by Catalytic Electropolymerization on Cu/Au Interdigital Electrodes

Nanostructured conductive polypyrrole has been prepared electrochemically on the surfaces of Cu/Au interdigital electrodes in the presence of Fe(II) as catalyst and ClO₄^? as anion dopant by using constant potential amperometry and cyclic voltammetry. The morphology of the conducting films was examined by field emission scanning electron microscopy, indicating a dependence from the processing technique. The synthesized polymer was used to investigate the properties of the gas sensing ability. The effect of the catalyst concentration on the oxidation mechanism of pyrrole was discussed. The PPy‐ClO₄ gas sensors had demonstrated fast response time and high sensitivity to VOCs.     

聚吡咯对Cu(II)的催化还原作用

以对甲苯磺酸钠为掺杂剂在不锈钢(SS)电极表面恒电位合成聚吡咯(PPy)修饰膜, 采用恒电位和动电位对Cu(II)的还原效果进行了研究, 并与不锈钢电极进行了对比. 结果表明, 由于聚吡咯的催化作用, 聚吡咯修饰电极对Cu(II)还原效率高于不锈钢电极; 聚吡咯膜对析氢有明显的抑制作用, 因此电流效率远远高于不锈钢电极, 这是采用聚吡咯进行电化学还原的明显优势. 通过在不同浓度Cu(II)酸性溶液中的循环伏安行为讨论了聚吡咯对Cu(II)的还原作用机理.     

Electrochemical supercapacitive properties of polypyrrole thin films: influence of the electropolymerization methods

A detailed study of the effects of different electropolymerization methods on the supercapacitive properties of polypyrrole (PPy) thin films deposited on carbon cloth is reported. Deposition mechanisms of PPy thin films through cyclic voltammetry (CV), potentiostatic (PS), and galvanostatic (GS) modes have been analyzed. The resulting PPy thin films have been characterized by X-ray photoelectron spectroscopy (XPS), SEM, and TEM. The electrochemical properties of PPy thin films were investigated by cyclic voltammetry and galvanostatic charge/discharge. The results showed that the different electrodeposition modes of synthesis significantly affect the supercapacitive properties of PPy thin films. Among different modes of electrodeposition, PPy synthesized by a potentiostatic mode exhibits maximum specific capacitance of 166 F/g with specific energy of 13 Wh/kg; this is attributed to equivalent proportions of the oxidized and neutral states of PPy. Thus, these results provide a useful orientation for the use of optimized electrodeposition modes for the growth of PPy thin films to be applied as electrode material in supercapacitors.     

Fabrication and Properties of Conducting Polypyrrole/SWNT‐PABS Composite Films and Nanotubes

We report the electropolymerization and characterization of polypyrrole films doped with poly(m‐aminobenzene sulfonic acid (PABS) functionalized single‐walled nanotubes (SWNT) (PPy/SWNT‐PABS). The negatively charged water‐soluble SWNT‐PABS served as anionic dopant during the electropolymerization to synthesize PPy/SWNT‐PABS composite films. The synthetic, morphological and electrical properties of PPy/SWNT‐PABS films and chloride doped polypyrrole (PPy/Cl) films were compared. Characterization was performed by cyclic voltammetry, atomic force microscopy (AFM), scanning electron microscopy (SEM) and Raman spectroscopy. SEM and AFM images revealed that the incorporation of SWNT‐PABS significantly altered the morphology of the PPy. Cyclic voltammetry showed improved electrochemical properties of PPy/SWNT‐PABS films as compared to PPy/Cl films. Raman Spectroscopy confirmed the presence of SWNT‐PABS within composite films. Field effect transistor (FET) and electrical characterization studies show that the incorporation of the SWNT‐PABS increased the electronic performance of PPy/SWNT‐PABS films when compared to PPy/Cl films. Finally, we fabricated PPy/SWNT‐PABS nanotubes which may lead to potential applications to sensors and other electronic devices.     

Interaction of metal ions with polypyrrole on polyacrylic acid matrix

The oxidative matrix polymerization of pyrrole (Py) by Fe(III), Cu(II), Ni(II), Co(II), and Zn(II) in the presence of polyacrylic acid (PAA) was studied and water‐soluble products along with insoluble products were obtained. The metal (Me) content of the insoluble part was determined by using atomic absorption spectroscopy (AAS). The effects of the oxidation potential of Me ions and ligands on the aggregation of polypyrrole (PPy) on the matrix polymer were measured by ultraviolet (UV)‐visible spectra. These findings also were checked by cyclic voltammetry (CV) measurements on PAA–Cu and PAA–PPy–Cu interactions. The conductometric titration results of PAA–PPy–Me ternary solutions were explained in the light of the interaction of Me ions with Py to polymerize on the PAA matrix resulting in some free carboxyl groups with a possibility of having Me–polymer complexes and a ternary complex (PAA–Me–PPy). The insoluble products were characterized by Fourier transform infrared (FTIR), elemental analysis, scanning electron microscopy (SEM), and four point probe conductivity measurements. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1115–1123, 1999     

离子液体中吡咯的电化学聚合及性质研究

以1-丁基-3-甲基咪唑六氟磷酸盐离子液体作为溶剂和支持电解质,分别在铂电极和导电玻璃电极上电化学聚合得到了聚吡咯,聚合过程中发现,在离子液体中聚合的循环伏安图,其电流的变化和传统有机溶剂中的不同,通过交流阻抗技术研究了修饰电极的电化学性质,采用在线紫外、拉曼、红外谱对聚吡咯进行了光谱表征,得到了聚吡咯的特征峰,采用扫描电镜研究了聚合物的形貌。最后将修饰电极应用到了对对苯二酚的催化反应当中,显示了一定的催化作用。     

Polypyrrole on self-assembled monolayers of a pyrrolyl lipoic acid derivative—electrosynthesis and polymer film characterization

The electropolymerization of pyrrole on gold modified by a self-assembled monolayer (SAM) of a pyrrolyl lipoic acid derivative was investigated in detail and the results compared to those obtained on bare substrates. Both under potentiostatic and potentiodynamic control, a slight blocking action of the underlying SAM could be observed for the initial stages of polymer growth but thereafter the electrochemical features were similar to those collected for polypyrrole (PPy) deposition on bare gold. The morphology and structure of PPy films formed on the SAMs were characterized by atomic force microscopy and X-ray diffraction, which revealed that those polymer properties are much more influenced by the electrochemical mode of preparation, than by the underlying SAMs. While, when compared to PPy on bare gold, no effect has been detected on thin layers deposited at constant potential, surface areas with rather irregular morphology, as well as a small but beneficial influence in inducing order on the first few layers of the polymer film, have been observed on similar films formed by cyclic voltammetry. The typical globular morphology of PPy has always been observed for relatively thick layers in which the redox behavior, analyzed by in situ AFM, showed an increase in volume of the polymer nodules upon reduction, largely due to the SAM reorganization induced by the applied potential.     

In situ FTIR spectroscopy study of the break-in phenomenon observed for PPy/PVS films in acetonitrile

The in situ Fourier transform infrared (in situ FTIR) technique was used for the first time to investigate the break-in phenomenon observed for polypyrrole/poly(vinyl sulfonate) (PPy/PVS) films in acetonitrile containing 0.1 M LiClO(4). Consecutive potential scans provided a continuous increase of the infrared band intensities, simultaneous to an increase observed in the charge involved in the voltammetric peaks, suggesting a rise in the number of the polymeric chains participating in the infrared signal at the same time as the electroactive participants increase in the redox process. Moreover, in situ FTIR spectra evidence that the new infrared-activated chains in each voltammetric cycle adopt the same polymeric structure achieved by the chains activated in the initial cycles. However, if we achieve a cathodic potential limit of -2.1 V (vs Ag/AgCl), a restructuring of the polymeric morphology is observed. In situ FTIR spectra obtained for PPy/ClO(4) films under the same conditions pointed to a steady-state behavior from the very early voltammetric scans. Moreover, the intensities of FTIR bands obtained for PPy/ClO(4) films in the early voltammetric cycles are much higher than those obtained for PPy/PVS films after several potential scans. Only when high cathodic and high anodic potential limits were used for the consecutive cycles did the FTIR band intensities from PPy/PVS become similar to those obtained from PPy/ClO(4), indicating that in both films a similar number of polymeric chains were infrared active. Polarization at a high anodic potential (+1.3 V vs Ag/AgCl) produced overoxidation of the polymer appearing characteristic 1725 cm(-1) band assigned to the formation of carbonyl groups. Furthermore, the approximately 1540 cm(-1) band shifted to higher wavenumbers, indicating that overoxidation reduced the length of conjugated chains in the polypyrrole.     

Preparation of conductive,flexible and transparent films by in situ deposition of polypyrrole nanoparticles on polyethylene terephthalate

In this study polypyrrole (PPy) nanoparticles were deposited as a thin film on the modified surface of polyethyleneterephthalate (PET) by in situ chemical polymerization in the presence of sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (DBSNa) and mixture of them as the surfactant. The surface of PET was modified by KOH before deposition and was investigated for conductivity and adhesion of PPy nanoparticles to PET. Resulting conductive flexible films were characterized by UV–Vis spectroscopy, fieldemission scanning electron microscopy, contact angle measurements and four-point-probe technique for conductivity. Direct morphological observation (FESEM) and electrical measurements indicated that the morphology, conductivity and the nature of deposited PPy films depend on surfactant, surface modification of PET and monomer concentration. In optimized process condition, uniform conductive films of PPy were obtained with good adhesion to PET.     

Application of Al2O3 in the electrosynthesis of polypyrrole with fuzzy morphology—Microtentacle

Polypyrrole (PPy) thin films were electrochemically polymerized onto the electrode surface. In this study alumina was used as the template and PPy film was prepared by electrochemical polymerization using Al/Al₂O₃ as the working electrode. Surface morphology of PPy was investigated by scanning electron microscopy (SEM) and the results revealed that the application of the template resulted in PPy with fantastic surface morphology which was called microtentacle and the length of the tentacle could reach 15 µm. The morphology can evidently increase the roughness, thus the surface area of the electrode substrate, and provide an intimate contact with the surrounding brain tissue compared to the hard, stiff metal surface. Relationship between PPy morphology and electrochemical polymerization parameters, such as polymerization time, was investigated. The study provided a fundamental method to prepare a PPy‐modified electrode with high surface area. Potential application of the study is proposed. Copyright © 2007 John Wiley & Sons, Ltd.     

Polymerization and characterization of high conductivity and good adhension polypyrrole films for electromagnetic interference shielding

<正>Polypyrrole(PPy) shows a favorable application in the electromagnetic interference(EMI) shielding due to its good electrical conductivity and outstanding air stability.Conducting PPy films with high conductivity and good adhesion were successfully polymerized on the surface of insulating epoxy resin substrates using chemical polymerization.The factors affecting the properties of PPy films,such as the surface morphology,adhesion between PPy film and substrate,electrical conductivity,EMI shielding effectiveness(SE),were investigated.The adhesion was improved significantly through a three-step surface pretreatment of epoxy resin substrates including removing impurities,roughening,and surface modification with silane coupling agent.An enhancement in the conductivity of PPy films of about one order of magnitude was achieved by adding dopant in FeCl_3 solution.The higher the conductivity,the better the shielding effectiveness.Taking sodium p-toluenesulfonate doped PPy film as example,EMI SE was in the practically useful range of about 30 dB over a wide frequency range from 30 MHz to 1500 MHz.The PPy film samples were characterized by scanning electron microscopy (SEM),infrared spectra(IR),X-ray photoelectron spectroscopy(XPS) and the flange coaxial transmission device.The fourpoint probe method was used to measure conductivity of PPy films.     

Engineering a Cu‐MOF Nano‐Catalyst by using Post‐Synthetic Modification for the Preparation of 5‐Substituted 1H‐Tetrazoles

A new nano scale Cu‐MOF has been obtained via post‐synthetic metalation by immersing a Zn‐MOF as a template in DMF solutions of copper(II) salts. The Cu‐MOF serves as recyclable nano‐catalyst for the preparation of 5‐substituted 1H‐tetrazoles via [3 + 2] cycloaddition reaction of various nitriles and sodium azide in a green medium (PEG). The post‐synthetic metalated MOF were characterized by FT‐IR spectroscopy, powder X‐ray diffraction (PXRD), atomic absorption spectroscopy (AAS), and energy dispersive X‐ray spectroscopy (EDX) techniques. The morphology and size of the nano‐catalyst were determined by field emission scanning electron microscopy (FE‐SEM).     

Enhancing electrochromic contrast and redox stability of nanostructure polypyrrole film doped by heparin as polyanion in different solvents

Heparin‐doped polypyrrole (PPy‐Hep) and ‐doped polypyrrole (PPy‐ClO₄) films are synthesized onto FTO‐coated glass electrode in a potentiostatic electrochemical process with the aim of producing uniform, transparent, and adherent coating. The resultant polymers are characterized via cyclic voltammetry, scanning electron microscopy (SEM), and UV–vis absorption spectroscopy. SEM study indicates that the PPy‐Hep film to be composed of a continuous interlinked network of quasi spherical grains (50–80 nm in dimensions). The electrochromic properties of PPy‐Hep and PPy‐ClO₄ polymer films are compared to spectroelectrochemistry and switching studies. The effect of different solvents (water, propylene carbonate, and acetonitrile) on the electrochromic features of electropolymerized polymers has been investigated, and we find a very significant solvent effect. PPy‐Hep film exhibits switching time of 1 s and the maximum transmittance contrast (ΔT%) is 48% at 800 nm in water. In addition, presence of Hep causes drastic enhancement of electro‐optical stability of PPy. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3365–3371     

In vitro cytotoxic and apoptotic effect of vic‐dioxime ligand and its metal complexes

In this study, vic‐dioxime ligand, (1E,2E)‐2‐(hydroxyimino)‐N′‐[(1E)‐2‐oxo‐2‐phenylethylidene]ethanehydroximohydrazide (LH₂), and its Cu (II) and Ni (II) transition metal complexes were synthesized and characterized using analytical and spectroscopic techniques. Furthermore, in vitro cytotoxic and apoptotic effects of this vic‐dioxime ligand and its Cu (II) and Ni (II) complexes on Caco‐2 heterogeneous human epithelial colorectal adenocarcinoma cells were evaluated. The effect of the vic‐dioxime ligand and its Ni (II) and Cu (II) complexes in combination with Campto on the cells was also investigated. The cytotoxicity test was carried using the MTT assay, and the apoptotic effect was tested by DNA diffusion assay. Campto was used as a standard anti‐cancer drug, Caco‐2 cancer cells treated with dimethylsulfoxide acted as solvent control, and human peripheral lymphocytes were used as control. The ligand and its complexes exhibit concentration‐dependent cytotoxic and apoptotic behavior. The ligand induces the weakest cytotoxic and apoptotic effects on both Caco‐2 cancer cells and lymphocytes. The Ni (II) complex of ligand induces high cytotoxic and apoptotic effects on both Caco‐2 cancer cells and lymphocytes. The Cu (II) complex of ligand has high cytotoxic and apoptotic effects on Caco‐2, but weak cytotoxic and apoptotic effects on lymphocytes. The cytotoxic and apoptotic effects of the ligand and its Ni (II) and Cu (II) complexes were found to be concentration dependent, i.e. the higher the concentration is the more cytotoxic it will be. The present findings suggest that Cu (II) complex has the potential to act as a promising anti‐cancer compound against Caco‐2 colon cancer cells.     

Functionalization of superparamagnetic Fe3O4@SiO2 nanoparticles with a Cu(II) binuclear Schiff base complex as an efficient and reusable nanomagnetic catalyst for N‐arylation of α‐amino acids and nitrogen‐containing heterocycles with aryl halides

Fe₃O₄@SiO₂ nanoparticles was functionalized with a binuclear Schiff base Cu(II)‐complex (Fe₃O₄@SiO₂/Schiff base‐Cu(II) NPs) and used as an effective magnetic hetereogeneous nanocatalyst for the N‐arylation of α‐amino acids and nitrogen‐containig heterocycles. The catalyst, Fe₃O₄@SiO₂/Schiff base‐Cu(II) NPs, was characterized by Fourier transform infrared (FTIR) and ultraviolet‐visible (UV‐vis) analyses step by step. Size, morphology, and size distribution of the nanocatalyst were studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and dynamic light scatterings (DLS) analyses, respectively. The structure of Fe₃O₄ nanoparticles was checked by X‐ray diffraction (XRD) technique. Furthermore, the magnetic properties of the nanocatalyst were investigated by vibrating sample magnetometer (VSM) analysis. Loading content as well as leaching amounts of copper supported by the catalyst was measured by inductive coupled plasma (ICP) analysis. Also, thermal studies of the nanocatalyst was studied by thermal gravimetric analysis (TGA) instrument. X‐ray photoelectron spectroscopy (XPS) analysis of the catalyst revealed that the copper sites are in +2 oxidation state. The Fe₃O₄@SiO₂/Schiff base‐Cu(II) complex was found to be an effective catalyst for C–N cross‐coupling reactions, which high to excellent yields were achieved for α‐amino acids as well as N‐hetereocyclic compounds. Easy recoverability of the catalyst by an external magnet, reusability up to eight runs without significant loss of activity, and its well stability during the reaction are among the other highlights of this catalyst.     

In situ polymerization and morphology of polypyrrole obtained in water‐soluble polymer templates

Several water‐soluble polymers were used as templates for the in situ polymerization of pyrrole to determine their effect on the generation of nanosized polypyrrole (PPy) particles. The polymers used include: polyvinyl alcohol (PVA), polyethylene oxide (PEO), poly(vinyl butyral), polystyrene sulfonic acid, poly(ethylene‐alt‐maleic anhydride) (PEMA), poly(octadecene‐alt‐maleic anhydride), poly(N‐vinyl pyrrolidone), poly(vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate), poly(N‐isopropyl acrylamide), poly(ethylene oxide‐block‐propylene oxide), hydroxypropyl methyl cellulose, and guar gum. The oxidative polymerization of pyrrole was carried out with FeCl₃ as an oxidant. The morphology of PPy particles obtained after drying the resulting aqueous dispersions was examined by optical microscopy, and selected samples were further analyzed via atomic force microscopy. Among the template polymers, PVA was the most efficient in generating stable dispersions of PPy nanospheres in water, followed by PEO and PEMA. The average size of PPy nanospheres was in the range of 160 nm and found to depend on the molecular weight and concentration of PVA. Model reactions and kinetics of the polymerization reaction of pyrrole in PVA were carried out by hydrogen ¹H NMR spectroscopy using ammonium persulfate as an oxidant. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polypyrrole electrodeposition on inorganic semiconductors CuInSe2 and CuInS2 for photovoltaic applications

Thin polypyrrole (PPy) layers with an average thickness of about 0.5 μm were deposited, using potentiostatic and galvanostatic techniques, on CuInSe₂ (CISe) structures prepared electrochemically on glass/ITO substrates and on CuInS₂ (CIS) structures fabricated on Cu tape substrates. The polymer layer of p-type is considered as an alternative to the traditional buffer layer and window layer in the conventional cell structure. The deposition proceeded from an aqueous solution containing sodium naphthalene-2-sulfonate as a dopant. In order to prepare stable PPy films of high quality with a good adherence to the surface of inorganic semiconductors CIS and CISe, the optimal concentrations of reagents, current densities and electrodepositing potentials were selected experimentally. Electrochemical polymerization of pyrrole to PPy on CIS surfaces is faster under white light irradiation and the polymerisation starts at lower potential than in the dark. Significant photovoltage and photocurrent of the fabricated CISe/PPy and CIS/PPy structures have been observed under standard white light illumination.     

Preparation and characterization of Cu (II) supported on poly(8‐hydroxyquinoline‐p‐styrene sulphonate) and its application as catalyst for the synthesis of hexahydroquinolines

Cu ( II ) supported on poly(8‐hydroxyquinoline‐p‐styrenesulfonate) (Cu ( II )@PHQSS) was prepared and fully characterized by the different techniques including fourier transform infrared spectroscopy (FT‐IR), ¹H NMR, ¹³C NMR, thermal gravimetric analysis (TGA), differential thermal gravimetric (DTG), differential thermal analysis (DTA), scanning electron microscope (SEM) and energy dispersive X‐ray analysis (EDS). Afterward, the Cu ( II )@PHQSS as nanostructured catalyst was used as catalyst for the synthesis of hexahydroquinolines.     

Selective Electrochemical Analysis of Various Metal Ions at an EDTA Bonded Conducting Polymer Modified Electrode

An EDTA‐bonded conducting polymer modified electrode was prepared and characterized by FT‐IR. The modified electrode was used for the selective electrochemical analysis of various trace metal ions such as, Cu(II), Hg(II), Pb(II), Co(II), Ni(II), Fe(II), Cd(II), and Zn(II) at the different pHs by linear sweep and square wave voltammetry. Dynamic ranges were obtained using square wave voltammetry from 0.1 μM to 10.0 μM for Co(II), Ni(II), Cd(II), Fe(II), and Zn(II) and 0.5 nM to 20 nM for Cu(II), Hg(II), and Pb(II) after 10 min of preconcentration. The detection limits were determined to be 0.1 nM, 0.3 nM, 0.4 nM, 50.0 nM, 60.0 nM, 65.0 nM, 80.0 nM, and 90.0 nM for Cu(II), Hg(II), Pb(II), Co(II), Ni(II), Cd(II), Fe(II), and Zn(II), respectively. The technique offers an excellent way for the selective trace determination of various heavy metal ions in a solution.     

Ultra low field emission characteristics of chloride doped polypyrrole films

Field emission characteristics of chloride doped polypyrrole (Cl‐PPy) films have been investigated. For this purpose, freestanding Cl‐PPy films have been synthesized by interfacial polymerization from two different monomer (pyrrole) concentrations (1 and 0.1 M), keeping the monomer to oxidant (FeCl₃) concentration ratio equal to 1. The surface morphology of these Cl‐PPy films, as revealed from scanning electron microscopy, was found to be granular in nature. The average grain size of films prepared using 1 and 0.1 M pyrrole concentrations were ～2.5 and ～1 µm, respectively. The measured threshold field, that is, field required to draw an emission current density of 10 µA/cm², for these two films were 0.27 and 0.15 V/µm, respectively. From these films, a maximum current density of 1 mA/cm² could be drawn at an electric field of 0.42 and 0.29 V/µm, respectively. The field emission current (investigated at a preset value of 1 µA) was found to be very stable up to 3h, suggesting utility of Cl‐PPy films as a novel material for field emission based applications. Copyright © 2010 John Wiley & Sons, Ltd.