Polypyrrole based materials

In all cases, the films were obtained by oxidative electropolymerization of the cited substituted complexes from organic or aqueous solutions. The mechanism of metalloporphyrin Him formation was suggested to be a radical-cation induced polymerization of the substituents on the periphery of the macrocycle. As it was reported for the case of polypyrrole-based materials ", cyclic voltammetry and UV-visible spectroscopy with optically transparent electrodes were extensively used to provide information on the polymeric films (electroactivity, photometric properties, chemical stability, conductivity, etc.). Based on the available data, it appears that the electrochemical polymerization of the substituted complexes leads to well-structured multilayer films. It also appears that the low conductivity of the formed films, combined with the cross-linking effects due to the steric hindrance induced by the macrocyclic Ugand, confers to these materials a certain number of limitations such as the limited continuous growth of the polymers due to the absence of electronic conductivity of the films. Indeed, the charge transport in many of these films acts only by electron-hopping process between porphyrin sites. 

Solid-state ion sensors with conducting polymers as sensing membranes have also proved useful in some applications. Of particular importance are the pH sensors based on polyaniline that can be also applied in non-aqueous solutions. Polypyrrole-based sensors for nitrate also show great promise for water analysis. However, in addition to these two excellent examples, a large number of functionalized conducting polymers have been synthesized already, and these materials may offer unique possibilities for fabrication of durable, miniaturized ion sensors. 

A solid-state solar cell was assembled with an ionic liquid—l-ethyl-3-methylimidazolium bis(trifluoromethanesulfone)amide (EMITFSA) containing 0.2 M lithium bis(trifluoromethanesulfone)amide and 0.2 M 4-tert-butylpyridine—as the electrolyte and Au or Pt sputtered film as the cathode.51,52 The in situ PEP of polypyrrole and PEDOT allows efficient hole transport between the ruthenium dye and the hole conducting polymer, which was facilitated by the improved electronic interaction of the HOMO of the ruthenium dye and the conduction band of the hole transport material. The best photovoltaic result ( 7p=0.62 %, 7SC=104 pA/cm2, FOC=0.716 V, and FF=0.78) was obtained from the ruthenium dye 5 with polypyrrole as the hole transport layer and the carbon-based counterelectrode under 10 mW/cm2 illumination. The use of carbon-based materials has improved the electric connectivity between the hole transport layer and the electrode.51... 

Work with PPy and PAni has reached the industrial stage. Bridgestone-Seiko has been selling coin-shaped 3-V polyaniline-based batteries for 5 years (1987-1992), and polypyrrole-based batteries were developed by Varta/BASF in the same period. Such batteries have lower energy densities than those of conventional batteries, but they are superior in terms of selfdischarge. The main characteristics of a typical PAni battery are compared to those of lead and Cd-Ni batteries in Table 4. The values mentioned for energy density and electric capacity density refer to the active material alone. 

C. Visy, E. Pinter, T. FuUei, and R. Patakfalvi, Characterization of electronically conducting polypyrrole based composite materials, Synth. Met., 152, 13-16 (2005). 

Polymer-polymer composite, 7-34 Polymorphism, 17-8, 17-12, 17-29-17-30 Polypentafiilvalene, 12-5 Polyphenylene-based materials, 5-2, 5-15 Polypyrrole (PPy), 7-17, 7-35-7-36, 7-38-7-39, 8-1-8-80,... 

The capability of polypyrrole to be reversibly doped and dedoped by electrochemical methods makes this electroactive material adequate for the construction of rechargeable batteries [181-185]. The electroactive polymer can be either the anode or the cathode of the cell, although construction of anodes is most common, due to difficulties in inserting negative charges into polyheterocycles. Technical factors such as cyclability, energy density, and stability have to be optimized in the future, before commercial application of polypyrrole-based batteries. 

Berdichevsky Y, Lo Y-H (2004) Polymer microvalve based on anisotropic expansion of polypyrrole. In Materials Research Society symposium- proceedings, 2003, vol 782, Materials Research Society, Boston, p A4.4.1... 

Three types of materials, metal oxide semiconductors such as ZnO and SnOa, conducting polymers such as polyanUine and polypyrrole, and carbon-based materials such as carbon nanotubes (CNTs) and graphene, have shown significant performance benefit for the development of 1-D- and 2-D-based sensors for VOCs (Table 14.3). Until recently, the development of 1-D nanostructure-based VOC sensor using the abovementioned materials was slow because of challenges in the synthesis and fabrication of these nanostructures with controlled dimensions, morphology, and purity. 

A large number of different pyrrole-based polymers have now been electrochemically synthesised, using a variety of conditions, and these are summarised in Table 2, although it should be noted that the size of this field and its rate of growth mean that it is impossible to make such a table completely comprehensive, and that reports of related new materials, particularly of copolymers incorporating pyrrole are continually appearing in the literature. Water-soluble polypyrroles have also recently been reported [246],... 

Skotheim et al. [286, 357, 362] have performed in situ electrochemistry and XPS measurements using a solid polymer electrolyte (based on poly (ethylene oxide) (PEO) [363]), which provides a large window of electrochemical stability and overcomes many of the problems associated with UHV electrochemistrty. The use of PEO as an electrolyte has also been investigated by Prosperi et al. [364] who found slow diffusion of the dopant at room temperature as would be expected, and Watanabe et al. have also produced polypyrrole/solid polymer electrolyte composites [365], The electrochemistry of chemically prepared polypyrrole powders has also been investigated using carbon paste electrodes [356, 366] with similar results to those found for electrochemically-prepared material. 

Furthermore, the utilization of preformed films of polypyrrole functionalized by suitable monomeric ruthenium complexes allows the circumvention of problems due to the moderate stability of these complexes to aerial oxidation when free in solution. A similar CO/HCOO-selectivity with regards to the substitution of the V-pyrrole-bpy ligand by an electron-with-drawing group is retained in those composite materials.98 The related osmium-based redox-active polymer [Os°(bpy)(CO)2] was prepared, and is also an excellent electrocatalyst for the reduction of C02 in aqueous media.99 However, the selectivity toward CO vs. HCOO- production is lower. 

Electronically conducting polymers (ECPs) such as polyaniline (PANI), polypyrrole (PPy) and po 1 y(3.4-cthy 1 cncdi oxyth iophcnc) (PEDOT) have been applied in supercapacitors, due to their excellent electrochemical properties and lower cost than other ECPs. We demonstrated that multi-walled carbon nanotubes (CNTs) prepared by catalytic decomposition of acetylene in a solid solution are very effective conductivity additives in composite materials based on ECPs. In this paper, we show that a successful application of ECPs in supercapacitor technologies could be possible only in an asymmetric configuration, i.e. with electrodes of different nature. 

Joshi PP, Merchant SA, Wang YD, Schmidtke DW (2005). MEMS sensor material based on polypyrrole-carbon nanotube nanocomposite film deposition and characterization. J. Micromech. Microengin. 5 2019-2027. 

Similar approach has also been taken by Ferain and Legras [133,137,138] and De Pra et al. [139] to produce nanostructured materials based on the template of the membrane with etched pores. Polycarbonate film was also of use as the base membrane of the template, and micro- and nanopores were formed by precise control of the etching procedure. Their most resent report showed the successful formation of ultrasmall pores and electrodeposited materials of which sizes were as much as 20 nm [139]. Another attractive point of these studies is the deposited materials in the etched pores. Electrochemical polymerization of conjugated polymer materials was demonstrated in these studies, and the nanowires based on polypyrrole or polyaniline were formed with a fairly cylindrical shape reflecting the side wall structure of the etched pores. Figure 10 indicates the shape of the polypyrrole microwires with their dimension changes by the limitation of the thickness of the template. 

In recent years the electrochemistry of the enzyme membrane has been a subject of great interest due to its significance in both theories and practical applications to biosensors (i-5). Since the enzyme electrode was first proposed and prepared by Clark et al. (6) and Updike et al. (7), enzyme-based biosensors have become a widely interested research field. Research efforts have been directed toward improved designs of the electrode and the necessary membrane materials required for the proper operation of sensors. Different methods have been developed for immobilizing the enzyme on the electrode surface, such as covalent and adsorptive couplings (8-12) of the enzymes to the electrode surface, entrapment of the enzymes in the carbon paste mixture (13 etc. The entrapment of the enzyme into a conducting polymer has become an attractive method (14-22) because of the conducting nature of the polymer matrix and of the easy preparation procedure of the enzyme electrode. The entrapment of enzymes in the polypyrrole film provides a simple way of enzyme immobilization for the construction of a biosensor. It is known that the PPy-... 

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