0000000000255687
AUTHOR
Mikhail A. Vorotyntsev
showing 31 related works from this author
Spatially limited diffusion coupled with ohmic potential drop and/or slow interfacial exchange: a new method to determine the diffusion time constant…
2004
Abstract We have analyzed chronoamperometric curves, I ( t ), after small-amplitude potential steps Δ E (PITT technique) for the model of linear diffusion of a species inside an electroactive film, taking into account ohmic effects in the external media (solution and electrode) as well as a finite rate of the interfacial exchange. For its short-time interval, t ≪ τ d ( τ d is the diffusion time constant, corresponding to unlimited diffusion from the interface), three approximate analytical expressions have been proposed. One of these represents an interpolation formula between the value of the current at the start of the diffusion process, I (0)=Δ E / R ext (after the end of the EDL chargin…
Electroactive polymeric material with condensed structure on the basis of magnesium(II) polyporphine
2011
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 …
2010
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…
Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides
2006
Abstract We have studied a reaction between the reduced form of titanocene dichloride (Cp 2 TiCl 2 ) and a group of organic halides: benzyl derivatives (4-X C 6 H 4 CH 2 Cl, X = H, NO 2 , CH 3 ; 4-X C 6 H 4 CH 2 Br, X = H, NO 2 , PhC(O); 4-X C 6 H 4 CH 2 SCN, X = H, NO 2 ) as well as three aryl halides (4-NO 2 C 6 H 4 Hal, Hal = Cl, Br; 4-CH 3 O-C 6 H 4 Cl). It has been shown that the electrochemical reduction of Cp 2 TiCl 2 in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Base…
Palladium nanoparticles–polypyrrole composite as an efficient catalyst for cyanation of aryl halides
2014
Abstract New palladium-polypyrrole (Pd/PPy) nanocomposites have been studied in cyanation of aryl halides with K 4 Fe(CN) 6 and showed high catalytic efficiency. Aryl iodides, bromides, and chlorides are active. The reaction can be performed both in organic solvents and in water; in the latter case, the catalyst was immobilized on graphite support. The cyanation of inactivated aryl chlorides is of special importance as only a few publications dealing with efficient cyanation of aryl chlorides are available, in which expensive and poisonous phosphine ligands and non-aqueous solvents are used. The influence of the morphology of the catalyst on its efficiency in cyanation was investigated, and…
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 su…
2014
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…
Memory effects in functionalized conducting polymer films: titanocene derivatized polypyrrole in contact with THF solutions
2003
Abstract Films with a polypyrrole matrix and pendant titanocene dichloride centers, p(Tc3Py), have been obtained by potentiostatic electropolymerization of the titanocene-pyrrolyl derivative, Tc3Py=Tc(CH 2 ) 3 NC 4 H 4 (Tc=Cl 2 TiCpCp′, Cp=C 5 H 5 , Cp′=C 5 H 4 ), in acetonitrile (AN) solutions on a Pt surface. The redox activity has been studied after the transfer of the film-coated electrode into the monomer-free solution of the same electrolyte, TBAPF 6 , in THF. Contrary to the case of AN or dichloromethane solutions, one can achieve a stable redox activity of the immobilized Tc centers in THF solutions during a series of cycles. A parallel between the redox properties of the Tc complex…
Palladium–Polypyrrole Nanoparticles-Catalyzed Sonogashira Coupling
2012
Abstract Palladium nanoparticles were encapsulated into polypyrrole globules via one-step one-pot redox reaction between tetraamminepal- ladium(ii) dichloride and pyrrole in water. Such a material is an active catalyst for the Sonogashira coupling of iodo- and bromo- arenes.
Electropolymerization of non-substituted Mg(II) porphine: Effects of proton acceptor addition
2015
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…
Extension of the potential intervals of high redox activity and electronic conductivity of polypyrrole films on electrode surface via their electroch…
2021
Abstract Thin polypyrrole films (thickness: about 30 nm) have been deposited at electrode surface via potentiostatic oxidation of dilute (1 mM) pyrrole solution in acetonitrile (AN). It has been shown that their subsequent treatment by means of multi-cycle voltammetry within a broad potential range (up to -2.0 V vs. Ag/Ag+ in AN) leads to their "activation", i.e. to a very strong extension of their redox response region in the negative direction as well as to almost uniform distribution of the redox activity within this potential range. Region of their high conductivity under in situ conditions has also extended significantly. Spectral and electrocatalytic properties of such PPy films befor…
Influence of chloride anions on the electrodeposition and electroactivity of the polymer matrix in polypyrrole, poly( N -methylpyrrole) and polypyrro…
2004
We report electrochemical studies on the influence of a small concentration of chloride ions on the electroactivity of the polymer matrix of polypyrrole (PPy), poly(N-methylpyrrole) [p(N-MePy)] and a poly(titanocene-propyl-pyrrole) derivative, p(Tc3Py) [Tc(CH2)3NC4H4; Tc=CpCp′TiCl2; Cp=C5H5; Cp′=C5H4] in acetonitrile (AN), tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). The polymer films were obtained on Pt disc electrodes from AN solutions of the monomers containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) as the supporting electrolyte and then transferred to the corresponding monomer-free solution. Studies in Cl−-containing solutions have shown that the p(Tc3Py) matrix…
Electron and proton conducting polymers: recent developments and prospects
2000
Abstract The most important topics of the rapidly developing field of conducting polymers are surveyed. Particular emphasis is laid on the problems of synthesis, structure, thermodynamics and kinetic behaviour of these systems. The relevant experiences, existing models and theories are outlined. Abundant examples of the growing applications are also discussed.
Charging process in electron conducting polymers: dimerization model
2001
Abstract Theory of the charging and discharging process in electron-conducting polymer films at an electrode surface has been presented. It is based on the concept of two coexisting subsystems at the polymer matrix, ‘usual’ sites P which can exchange with the electrode by the electronic charge in a quasi-reversible manner, and sites D where intermolecular bonds between neighboring polymer molecules can be formed. The charging and discharging of the latter subsystem may be realized along different reaction pathways, e.g. via the bond formation after the generation of two cation radicals within such site D in the course of the anodic scan while the bond dissociation may take place via a parti…
Electrochemical impedance spectroscopy of thin films with two mobile charge carriers: effects of the interfacial charging
1999
In the electrochemical systems containing an excess of the background electrolyte, the faradaic process and the interfacial (‘double-layer’) charging are coupled to the fluxes of different charge carriers, the former being related to the diffusional transport of electroactive entities while the latter being realized mostly by ions of the supporting electrolyte. As a result, the interfacial capacitance Cdl may simply be added in parallel to the faradaic impedance specific for each particular system (Randles & Ershler). This simple treatment is not justified in the absence of an indifferent electrolyte, if the same charged species take part in both the electrode reaction and the double layer …
Studies on the Reduction of [(C 5 Me 5 ) 2 Mo 2 O 5 ] in Methanol/Water/Acetate Solutions by On‐Line Electrochemical Flowcell and Electrospray Mass S…
2003
The complex [Cp*2Mo2O5] (Cp* = η5-C5Me5) and its electrochemical reduction products in acetic acid/acetate-buffered (pH = 4.0) water/methanol solutions were investigated by combined electrochemical (EC) flowcell and on-line electrospray ionization mass spectrometry (ESI-MS). Mono-, di-, tri-, and tetranuclear organometallic molybdenum oxides were identified in the starting solution. The effect of the relevant ESI-MS parameters (ionic mode, heated capillary voltage, and heated capillary temperature) and of the concentration on the observed distribution of ions in the mass spectrometer was studied in order to minimize side reactions in the ESI chamber. It was verified that reduction in the ES…
Polypyrrole–palladium nanoparticles composite as efficient catalyst for Suzuki–Miyaura coupling
2012
International audience; Synthesis of a new hybrid material (Pd/PPy) composed of polypyrrole globules with uniformly incorporated Pd nanoparticles via direct redox reaction between pyrrole and Pd(NH3)(4)Cl-2 in water has been recently reported (V.A. Zinovyeva, M.A.Vorotyntsev, I. Bezverkhyy, D. Chaumont, J.-C. Hierso, Adv. Funct. Mater. 21 (2011) 1064-1075). In the actual study, this procedure has been extended to synthesize a series of Pd/PPy powders with variable palladium content and morphological parameters. Depending on the monomer-to-oxidant ratio in reaction mixture, average diameters of Pd and PPy particles may change in the ranges of 1.25-1.45 and 27-62 nm, respectively, the Pd conc…
Redox properties of titanocene-pyrrole derivative and its electropolymerization
2001
A new titanocene dichloride derivative in which one cyclopentadienyl ligand (Cp) is functionalized with a pyrrolyl ring, Tc3Py (Cl2TiCpC5H4(CH2)3NC4H4), has been synthesized and characterized with NMR. Its redox properties have been studied by CV in acetonitrile (AN), tetrahydrofurane (THF) and dichloromethane (DCM), in comparison with unsubstituted titanocene dichloride (Tc) and pyrrole. Ti(IV/III) transition observed within the negative potential range is a quasi-reversible reaction in THF and DCM (but without a complete recuperation of the initial reagent in the back scan) while the reoxidation peak in AN is strongly shifted in the positive direction. These results are interpreted within…
Application of a Novel Refinement Method for Accurate Determination of Chemical Diffusion Coefficients in Electroactive Materials by Potential Step T…
2005
We describe application of a novel refinement method for an accurate determination of the chemical diffusion coefficient, D, and the generalized kinetic parameter, A, from experimental potentiostatic intermittent titration technique (PITT) data suited for a variety of electrochemically doped electroactive polymers and inorganic intercalation host materials. The proposed, simple, two-step refinement procedure, based on earlier derived analytical expressions for the PITT response, is exemplified by the analysis of chronoamperometric responses to small-amplitude potential perturbation for p- and n-doped poly(fluorenone-bithiophene) (PFDOBT-HH) thin film electrode. The initial p-doping and the …
Polypyrrole films functionalized with pendant titanocene dichloride complexes: Ellipsometric study of the electropolymerization process
2007
Electrochemical and ellipsometric methods have been used to study the electropolymerization process of a functionalized monomer, Tc3Py (in which pyrrole is covalently bonded with titanocene dichloride complex) on platinum electrode from a dilute monomer solution in acetonitrile. The deposition has been performed in the potentiodynamic regime. A new method for the acquisition and treatment of ellipsometric data has been proposed which allowed us to analyze the evolution of the film properties at each potential. The model of a single uniform layer was unable to describe the ellipsometric experimental observations with the necessary precision. A proper fitting of the data has been achieved con…
Mechanism of redox transformation of titanocene dichloride centers immobilized inside a polypyrrole matrix—EQCM and XPS evidences
2005
Abstract We report electrochemical quartz crystal microbalance (EQCM) results for electrodeposition of titanocene derivatized polypyrrole p(Tc3Py) films and redox transformation of polypyrrole matrix and titanocene centers immobilized in the film. Films of p(Tc3Py), Tc3Py = Tc(CH 2 ) 3 NC 4 H 4 (Tc = Cl 2 TiCpCp′, Cp = C 5 H 5 , Cp′ = C 5 H 4 ) were obtained from acetonitrile solutions of monomer on a Pt disc or thin Au layer evaporated on 10 MHz quartz crystals. Polymerization efficiency, derived from the slope of the change of resonant frequency as a function of the deposition charge ranged from 54% to 75%. A gradual loss of redox activity of Tc centers during consecutive redox cycles of …
Primary and secondary distributions after a small-amplitude potential step at disk electrode coated with conducting film
2011
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…
Highly Dispersed Palladium-Polypyrrole Nanocomposites: In-Water Synthesis and Application for Catalytic Arylation of Heteroaromatics by Direct C-H Bo…
2011
Pd@PPy hybrid catalytic materials are synthesized in water via redox polymerization reaction of pyrrole with [Pd(NH 3 ) 4 Cl 2 ]. The nanocomposites formed are composed of highly dispersed palladium particles which are either zerovalent or easily reducible, and are embedded in spherical polypyrrole globules. A unique combination of high palladium dispersion (NP size: 2.4 nm) and elevated palladium content (35 wt%) is obtained. The components of these novel nanocomposites are characterized by means of FTIR, XPS, XRD, SEM, and TEM microscopy techniques. The process of formation in solution is also monitored using UV-visible and DLS techniques. The application of these novel hybrid nanomateria…
Electrocatalytic properties of manganese and cobalt polyporphine films toward oxygen reduction reaction
2018
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…
Synthesis and Characterization of Palladium Nanoparticle/Polypyrrole Composites
2008
In this work, a simple non-template one-step method for the synthesis of 2.0−2.5 nm palladium nanoparticles encapsulated into a polypyrrole shell via direct redox reaction between palladium(II) acetate and pyrrole in acetonitrile medium is described. Palladium nanoparticles are found to be able to self-organize into spherical Pd/PPy composites. The size of the Pd/PPy composite particles and Pd content in the composite depend strongly on the concentration of the palladium salt component. The combination of elemental CHNS and thermogravimetric (TGA) analysis was used to determine a high (∼40 wt %) content of palladium, which is in a good agreement with EDX data. The process of Pd/PPy composit…
In situ UV-visible spectroelectrochemistry in the course of oxidative monomer electrolysis
2015
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…
Time−Difference Impedance Spectroscopy of Growing Films Containing a Single Mobile Charge Carrier, with Application to Surface Films on Li Electrodes
2000
In this paper we present a new approach to the analysis of electrochemical impedance spectroscopy (EIS) data for electrodes covered by passivating surface films that grow in time. The impedance of ...
One-stage periodical anodic-cathodic double pulse deposition of nanocomposite materials. Application to Prussian Blue/polypyrrole film coated electro…
2014
Abstract Novel electrochemical method of one-stage deposition of composite films on electrode surface has been proposed. The procedure includes a periodical series of potentiostatic or galvanostatic pulses of alternative polarity imposed at electrode in contact with a mixture of two solute precursors, one of which is able to generate a solid phase under its electrooxidation while another one is transformed into another solid phase under its electroreduction. Parameters of anodic and cathodic pulses (potential or current, pulse duration) may be chosen independently from one another, their relation allows one to vary the relative contents of components in the deposited composite. Thickness of…
Li-ion diffusion in Li_{x}Nb_{9}PO_{25}$
2013
Abstract Wadsley–Roth phase Li x Nb 9 PO 25 has been studied as a potential candidate for anode material of Li-ion batteries. Its crystal structure, which consists of ReO 3 -type blocks of NbO 6 octahedra connected with PO 4 tetrahedra, provides a good stability and performance during Li + insertion/removal. Li-ion chemical diffusion coefficient ( D chem ) in Li x Nb 9 PO 25 was determined by means of potentiostatic intermittent titration technique and electrochemical impedance spectroscopy. Different data treatments (classical Warburg equation or the model of an electrode system with ohmic potential drop and/or slow kinetics of the interfacial Li + ion transfer across the electrode/electro…
Physical origin of Na+/Cl− selectivity of tight junctions between epithelial cells. Nonlocal electrostatic approach
2020
Abstract Tight junctions (TJs) of epithelial cells play a key role in regulation of the ion exchange between NaCl solutions separated by the layer of these cells. Their functioning is based on a strong difference in the permeabilities of these channels for Na+ and Cl− ion migrational fluxes owing to specific properties of the protein network inside TJs. It has been assumed in this study that this phenomenon originates from combination of two effects related to this specific TJ protein (claudin) which segments are partially located inside the TJ space. First, their ionogenic groups create a negative charge distributed inside TJs, thus inducing a difference between the Na+ and Cl− concentrati…
Atomic force microscopy study of conducting polymer films near electrode's edge or grown on microband electrode
2013
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…
Electrosynthesis and properties of poly(3,4-ethylenedioxythiophene) films functionalized with titanocene dichloride complex
2006
Synthesis of a titanocene dichloride derivative functionalized with 3,4-etylenedioxythiophene group, Tc1EDOT (Cl 2TiCpC5H4(CH2) (3,4ethylenedioxythiophene)) has been described. Redox behavior of the monomer in tetrahydrofuran (THF), dichloromethane (DCM) and acetonitrile (AN) at different scan rates has been discussed in terms of different ability of these solvents to coordination with the reduced titanocene (Tc) complex and the solvation of Cl − anions. Electrooxidation of Tc1EDOT to get a conducting polymer film with immobilized titanocene dichloride centers and electrochemical properties of its polymer matrix in background acetonitrile solution have been compared with those of non-substi…