Investigation of electrochemical behavior of some dithiophosphonates in acetonitrile on the platinum and gold electrodes


Cekirdek P., Solak A. O. , Karakus M., Aydin A. , Yilmaz H.

ELECTROANALYSIS, cilt.18, ss.2314-2323, 2006 (SCI İndekslerine Giren Dergi) identifier identifier

  • Cilt numarası: 18 Konu: 23
  • Basım Tarihi: 2006
  • Doi Numarası: 10.1002/elan.200603669
  • Dergi Adı: ELECTROANALYSIS
  • Sayfa Sayıları: ss.2314-2323

Özet

Some dithiophosphonate derivatives were synthesized and the electrochemical reduction mechanism was investigated by cyclic voltammetry (CV), square wave voltammetry (SWV) and chronoamperometry (CA) in 0.1 M tetrabutylammoniumtetrafluoroborate (TBATFB) in acetonitrile at platinum (Pt) and gold (Au) electrodes. Dithiophosphonates showed a cyclic voltammetric reduction peak at about -1.1 V at Pt and -1.3 V at An electrode (vs. Ag/Ag+) in this media. It was also shown that dithiophosphonates can be determined quantitatively in acetonitrile using a calibration graph. The number of electrons transferred were calculated as 2 using ferrocene as a reference compound at the UME electrode. Mechanism of dithiophosphonates was also examined on Pt and An electrodes and electrochemical reduction of dithiophosphonates seems to follow an EC mechanism with an irreversible electron transfer step. The reaction product in the bulk electrolysis experiment was isolated and identified using proton-coupled P-31 NMR, C-13-NMR and IR spectroscopy. The adsorption tests for dithiophosphonates were revealed that no strong or weak adsorption phenomena exist on both Pt and Au electrodes. Simulation curves were acquired by DigiSim 3.03 version to investigate the reduction mechanism and to estimate the kinetic parameters for electrochemical and chemical steps.