0000000000262570
AUTHOR
Dmitry V. Konev
Electroactive polymeric material with condensed structure on the basis of magnesium(II) polyporphine
International audience; Previous publication of the authors presented evidences that electroch emical oxidation of Mg(II) porphine (fully unsubstituted porphyrin, MgP) in acetonitrile (AN) at a very low potential leads to deposition of films at electrode surface corresponding to typical electroactive polymers, with their reversible transition betwee n the electronconducting and insulating states depending on the electrode potential/oxidation level ("film of type I"). It is demonstrated in the actual publication that these films in contact with a monomer-free solution are subject to an irreversible transformation to quite a different material ("film of type II") under the influence of a high…
Magnesium(II) polyporphine: The first electron-conducting polymer with directly linked unsubstituted porphyrin units obtained by electrooxidation at a very low potential
Abstract Electrooxidation of magnesium(II) porphine, a totally unsubstituted porphyrin, in acetonitrile solution under potentiostatic or potentiodynamic regime leads to a polymer film at the electrode surface. Polymer deposition takes place at extremely low potential, several hundred mV less positive even compared to the deposition potential for pyrrole or EDOT (at identical monomer concentrations) in the same solvent. Film thickness can be controlled by the passed deposition charge. This material and its THF-soluble fraction have been characterized by various electrochemical methods as well as by UV–visible and IR spectroscopies, XPS, XRD and MALDI-TOF techniques. This analysis has allowed…
Synthesis of new electroactive polymers by ion-exchange replacement of Mg(II) by 2H+ or Zn(II) cations inside Mg(II) polyporphine film, with their subsequent electrochemical transformation to condensed-structure materials
Abstract It has been demonstrated that the treatment of the magnesium polyporphine of type I, pMgP-I, by trifluoroacetic acid in acetonitrile may be used to replace initial central Mg(II) cations inside the monomeric macrocycle units by protons, to get a new electroactive polymer, “free-base polyporphine of type I”, pH2P-I. In its turn, these inserted protons may be replaced by Zn(II) cations via the film treatment with zinc acetate in organic solvent, to get another new electroactive polymer, “zinc polyporphine of type I”, pZnP-I. These changes of central ions inside monomer units manifest themselves by characteristic modifications of their electroactive properties as well as of UV–visible…
Electropolymerization of non-substituted Mg(II) porphine: Effects of proton acceptor addition
Abstract Electropolymerization of unsubstituted magnesium porphine in acetonitrile solutions possessing various proton-accepting properties has been studied. The overall rate of the polymer-product accumulation on the electrode surface has been established to be limited by the deprotonation step of intermediate species. This conclusion is based on the observed influence of proton-accepting additives, water or 2,6-dimethylpyridine (lutidine), on the Mg-porphine electrooxidation process. Lutidine addition into the polymerization bath enables one to enhance strongly the rate of the film growth and the efficiency of this process increases more than by a factor of two, redox, electric conductivi…
Primary and secondary distributions after a small-amplitude potential step at disk electrode coated with conducting film
Abstract The set of equations and boundary conditions for the “primary potential/current distribution” after a small-amplitude potential step has been analyzed for a film-coated disk electrode in contact with an electrolyte. The solution of these equations provides the overall short-time resistance of this system, Rtot, which is determined by the short-time resistance of the electrolyte solution in contact with the bare disk electrode, Rs, and the short-time film resistance to the current passage in the normal direction, R f = L f / κ f π r o 2 (ro, disk radius; Lf, film thickness; κf, its specific conductivity). The deviation of Rtot from the sum of these resistances, Rs + Rf, originates f…
Electrocatalytic properties of manganese and cobalt polyporphine films toward oxygen reduction reaction
International audience; Novel member of polymetalloporphines, namely manganese polymetalloporphine of type I (pMnP-I) obtained by ion exchange from magnesium polyporphine of type I (pMgP-I) is reported for the first time and compared to its cobalt analogue (pCoP-I). Both polymer films have been obtained via two-step procedure: demetaladon of the pMgP-I electrode film via its exposure to trifluoroacetic acid solution, resulting in formation of the metal-free polyporphine of type I (pH(2)P-I) followed by electrochemically induced incorporation of Co or Mn ions from the acetonitrile solution of cobalt and manganese perchlorates. A further oxidative transformation of pCoP-I, polymer films has l…
In situ UV-visible spectroelectrochemistry in the course of oxidative monomer electrolysis
Abstract Novel method to characterize the macromolecuar structure of an electroactive polymer deposited via electrooxidation of the corresponding monomer on the electrode surface has been proposed. It is based on experimental determination of the number of electrons spent for oxidation of an initially solute monomer species which is used to calculate the number of covalent bonds linking each monomer unit with neighboring units inside the polymer. The former parameter is found by tracing simultaneously the variations of instantaneous values of the solute monomer concentration and of the passed charge in the course of the monomer oxidation electrolysis. This monomer concentration is establish…
Atomic force microscopy study of conducting polymer films near electrode's edge or grown on microband electrode
Abstract Polypyrrole (PPy) films of different thicknesses (within the range from 200 nm to 2.5 μm) were electrodeposited on two types of inhomogeneous substrates, single band and double-band Pt electrodes. Topographic images of the polymer layers were obtained by means of ex situ large-scale AFM technique to demonstrate how the propagation rates of the film growth above the electrode (in the normal direction to the electrode surface) and along the insulating surface surrounding the single- or double-band electrodes (in the horizontal direction) change with the deposition charge. It is proved that variations in the film thickness over the double band electrodes and progressive changes of the…