Methodology for Determination of the Key Parameters of Conjugated Polymer Electrodeposition,Based on a Combination of Spectroelectrochemistry and Electrochemical Quartz Crystal Microbalance

Russian Journal of Electrochemistry - Methodology based on a combination of experimental data obtained by in situ methods of spectroelectrochemistry and electrochemical quartz crystal microbalance...     

Efficiency of Pyrrole Electropolymerization under Various Conditions

The electrooxidative polymerization of pyrrole on the surface of a glassy carbon electrode was studied, while varying the solvent, the type and concentration of supporting electrolyte, redox mediator addition to the polymerization medium, and hydrodynamic conditions. The efficiency of polymerization was determined as the ratio of the charge of the redox response of the polymer film under the standard conditions to the total charge of film formation in the monomer solution. The above factors were varied to determine the conditions that allow minimization of the ratio in order to obtain the highest yield of the polymer product. This was achieved by using a combination of a redox mediator addition with active stirring of solution.

     

Spectroelectrochemical determination of the redox equivalent of magnesium porphine in the course of its electrooxidation

The spectroelectrochemical method has been applied for studying the electropolymerization of magnesium porphine with the aim to determine the number of electrons consumed per monomer molecule, which allows one to find out the number of bonds between the units in the resulting polymer. Based on the results, a conclusion has been made about the structure of macrochains of the basic representative of a new family of electroactive materials, magnesium porphine     

Quantum-chemical modeling of polypyrrole structure in neutral complexes with electron density acceptors

Quantum chemical approach has been applied for modeling the change in the conformation of the polypyrrole (PPy) chain both in its neutral and positively charged (doped) states due to its interaction with incorporated counterions. Polymer has been modeled by oligopyrrole molecule of 9–15 monomer units. It is shown that it is energetically favorable to reorient the pyrrole rings closest to the anion from trans to cis position. This reorientation leads to the formation of meanders which include 3–5 pyrrole rings per loop. Reduction in the loop size decreases the energy of interaction with the ion while an increase in the loop size reduces the number of attached ionic species accompanied by a slight change in their interaction energy with the PPy chain. The observed effect of polymer chain structuring in the presence of anions is proposed as a possible reason explaining the experimentally recorded broadening of the electroactivity potential region and the conductive state of the polypyrrole film on the electrode surface as a result of multiple repetitions of charge/discharge cycles of the polymer chain. Vibrational spectra of oligopyrrole complexes have been calculated, and prospects for experimental detection of predicted conformational states by IR spectroscopy are assessed.     

Electrochemical route to Co(II) polyporphine

Journal of Solid State Electrochemistry - Novel synthetic route towards electroactive films of Co(II) polyporphine has been elaborated. It is based on the electrochemical transformation of the...     

Electropolymerization of magnesium 5,15-di(<Emphasis Type="Italic">n</Emphasis>-methoxyphenyl)porphine

The process of electroxidative polymerization of magnesium 5,15-di(n-methoxyphenyl)porphine MgP(MeOPh)₂ is studied. The presence of substituents in positions 5 and 15 of the porphine macroring makes reactive two of its four meso positions, which allows new bonds to be formed only in the opposite positions 10 and 20. As a result, the process of electropolymerization of this substituted monomer at its oxidation can produce only linear chains, in contrast to unsubstituted magnesium porphine MgP for which the polymer structure can both be linear and contain zigzag and/or cruciform fragments.     

Electrochemical synthesis of polypyrrole in powder form

Journal of Solid State Electrochemistry - Novel approach to synthesis of conjugated oligomers/polymers is proposed. This approach combines all advantages of electrochemical methods: variation of...     

Hydrogen-Chlorate Electric Power Source: Feasibility of the Device,Discharge Characteristics and Modes of Operation

A power source based on the current-generating reaction of aqueous chlorate-to-chloride reduction by molecular hydrogen would provide as much as 1150 Wh per 1 L of reagent storage (for a combination of 700 atm compressed hydrogen and saturated aqueous solution of lithium chlorate) at room temperature, but direct electroreduction of chlorate only proceeds with unacceptably high overvoltages, even for the most catalytically active electrodes. In the present study, we experimentally demonstrated that this process can be performed via redox-mediator catalysis by intermediate products of chlorate reduction, owing to their participation in homogeneous com- and disproportionation reactions. A series of current–voltage and discharge characteristics were measured for hydrogen-chlorate membrane–electrode assembly (MEA) cells at various concentrations of chlorate and sulfuric acid under operando spectrophotometric monitoring of the electrolyte composition during the discharge. We established that chlorine dioxide (ClO₂) is the key intermediate product; its fraction in the electrolyte solution increases progressively, up to its maximum, equal to 0.4–0.6 of the initial amount of chlorate anions, whereas the ClO₂ amount decreases gradually to a zero value in the later stage. In most discharge experiments, the Faradaic yield exceeded 90% (maximal value: 99%), providing approximately 48% chemical energy storage-to-electricity conversion efficiency at maximal power of the discharge (max value: 402 mW/cm²). These results support prospect of a hydrogen-chlorate flow current generator as a highly specific energy-capacity source for airless media.     

Electrochemical synthesis of cobalt polyporphine films

A method for modification of the inert electrode surface with an electroactive polymeric film containing the CoN₄ catalytic site has been suggested and approved. The described approach affords the maximal content of the metal porphine moiety per unit weight of the coating. The classical method of introduction of an ion into the porphine macrocycle has been replaced by electrochemical polarization of an electrode with a metallated film in a dilute solution. The metalation efficiency has been demonstrated by the presence of changes in the current–voltage and spectral characteristics of the resulting polymeric films of the unsubstituted porphine pH₂P and cobalt polyporphine pCoP.