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Kinetics of Redox Processes in the Polymer Films of Ni(II) Salen Type Complexes.

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Bibliographic Details
Title: Kinetics of Redox Processes in the Polymer Films of Ni(II) Salen Type Complexes.
Authors: Tomczyk, Danuta1 danuta.tomczyk@chemia.uni.lodz.pl, Bukowski, Wiktor2, Bester, Karol2
Source: Journal of The Electrochemical Society. 2019, Vol. 166 Issue 6, pH194-H204. 11p.
Subjects: Conducting polymers, Polymer films, Oxidation-reduction reaction
Abstract: The voltammetry and chronocoulometry methods were used in the research of kinetics of redox processes occurring on electrodes modified with conductive polymers, derived from the following complexes: (±)-trans- N,N'-bis(salicylidene)- 1,2-cyclohexanediaminenickel(II) (poly[Ni(salcn)]), ((±)-trans-N,N'-bis(3,-methylsalicylidene)-1,2-cyclohexanediaminenickel(II) (poly[Ni(salcn(Me))]) and ((±)-trans-N,N'-bis(3,-tert-butylsalicylidene)-1,2-cyclohexanediaminenickel(II) (poly[Ni(salcn(Bu))]). Spectroelectrochemical method and chronopotentiometry were used to determine the mechanisms of redox processes. In poly[Ni(salcn)] and poly[Ni(salcn(Bu))] the ligand is oxidized, whereas in poly[Ni(salcn(Me))] both the ligand and the central ion are oxidized. The processes take place according to the EE mechanism. The poly[Ni(salcn)] and poly[Ni(salcn(Me))] films of thickness obtained as a result of 1-30 electropolymerization cycles, as well as poly[Ni(salcn(Bu))] of thickness obtained as a result of up to 150 cycles were studied. The investigated films of each complex are limited by surface processes, diffusion and surface-diffusion processes, depending on the film thickness. For the films that generate surface-diffusion processes, the boundaries of such processes have been determined. For the diffusion processes, the boundaries of semi-infinite diffusion regime and finite diffusion regime have been defined. On this basis, the cD1/2 value for anode and cathode processes providing semi-infinite diffusion conditions has been determined as a criterion for selection of the optimal conditions for modification of the electrodes. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
Description
Abstract:The voltammetry and chronocoulometry methods were used in the research of kinetics of redox processes occurring on electrodes modified with conductive polymers, derived from the following complexes: (±)-trans- N,N'-bis(salicylidene)- 1,2-cyclohexanediaminenickel(II) (poly[Ni(salcn)]), ((±)-trans-N,N'-bis(3,-methylsalicylidene)-1,2-cyclohexanediaminenickel(II) (poly[Ni(salcn(Me))]) and ((±)-trans-N,N'-bis(3,-tert-butylsalicylidene)-1,2-cyclohexanediaminenickel(II) (poly[Ni(salcn(Bu))]). Spectroelectrochemical method and chronopotentiometry were used to determine the mechanisms of redox processes. In poly[Ni(salcn)] and poly[Ni(salcn(Bu))] the ligand is oxidized, whereas in poly[Ni(salcn(Me))] both the ligand and the central ion are oxidized. The processes take place according to the EE mechanism. The poly[Ni(salcn)] and poly[Ni(salcn(Me))] films of thickness obtained as a result of 1-30 electropolymerization cycles, as well as poly[Ni(salcn(Bu))] of thickness obtained as a result of up to 150 cycles were studied. The investigated films of each complex are limited by surface processes, diffusion and surface-diffusion processes, depending on the film thickness. For the films that generate surface-diffusion processes, the boundaries of such processes have been determined. For the diffusion processes, the boundaries of semi-infinite diffusion regime and finite diffusion regime have been defined. On this basis, the cD1/2 value for anode and cathode processes providing semi-infinite diffusion conditions has been determined as a criterion for selection of the optimal conditions for modification of the electrodes. [ABSTRACT FROM AUTHOR]
ISSN:00134651
DOI:10.1149/2.0961906jes