A Systematic Study of the Mass Transport, Kinetic and Thermodynamic Properties of the FeIII/II Process at Glassy Carbon and Boron-Doped Diamond Electrodes

Mingyue Lin, Jiezhen Li, Dawei Pan, Alan M Bond, Jie Zhang

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The heterogeneous electron transfer kinetics (k0 values), mass transport and thermodynamic properties (E0 values) associated with the FeIII/II process have been determined in aqueous solutions containing 0.1 M HCl, HClO4, bis(trifluoromethanesulfonyl)imide (HNTf2) or 0.05 M silicotungstic acid (H4[α-SiW12O40]) supporting electrolytes. The diffusion coefficient (D) values for FeIII and FeII are dependent on the radius of the electrolyte anion and follow the order D(SiW12O40 4−) < D(NTf2 ) < D(ClO4 ) < D(Cl). The k0 values are found to be smaller at boron doped diamond (BDD) electrodes than glassy carbon (GC) electrodes, and influenced by the ion-pairing between electrolyte anions and FeIII and FeII. Based on the formal potential value, HNTf2 is found to be a more innocent electrolyte than commonly used HClO4 with regard to determine the true k0 values of the outer-sphere [Fe(H2O)6]3+/2+ process. Fourier transformed large amplitude alternating current voltammetry, which provides favorable signal to background ratio, was used to determine k0 values associated with the FeIII/II process in H4[α-SiW12O40] and HNTf2 electrolyte media at GC electrodes and probe the implications of the heterogeneity of the BDD electrode surface on the electrode kinetic determination in H4[α-SiW12O40] electrolyte media.

Original languageEnglish
Pages (from-to)421-430
Number of pages10
JournalElectrochimica Acta
Volume249
DOIs
Publication statusPublished - 20 Sep 2017

Keywords

  • electrode heterogeneity
  • electron transfer kinetics
  • Fe process
  • Fourier transformed alternating current voltammetry
  • medium effect

Cite this

@article{86359908bd9a4b88b90ca372d0b865f1,
title = "A Systematic Study of the Mass Transport, Kinetic and Thermodynamic Properties of the FeIII/II Process at Glassy Carbon and Boron-Doped Diamond Electrodes",
abstract = "The heterogeneous electron transfer kinetics (k0 values), mass transport and thermodynamic properties (E0 values) associated with the FeIII/II process have been determined in aqueous solutions containing 0.1 M HCl, HClO4, bis(trifluoromethanesulfonyl)imide (HNTf2) or 0.05 M silicotungstic acid (H4[α-SiW12O40]) supporting electrolytes. The diffusion coefficient (D) values for FeIII and FeII are dependent on the radius of the electrolyte anion and follow the order D(SiW12O40 4−) < D(NTf2 −) < D(ClO4 −) < D(Cl−). The k0 values are found to be smaller at boron doped diamond (BDD) electrodes than glassy carbon (GC) electrodes, and influenced by the ion-pairing between electrolyte anions and FeIII and FeII. Based on the formal potential value, HNTf2 is found to be a more innocent electrolyte than commonly used HClO4 with regard to determine the true k0 values of the outer-sphere [Fe(H2O)6]3+/2+ process. Fourier transformed large amplitude alternating current voltammetry, which provides favorable signal to background ratio, was used to determine k0 values associated with the FeIII/II process in H4[α-SiW12O40] and HNTf2 electrolyte media at GC electrodes and probe the implications of the heterogeneity of the BDD electrode surface on the electrode kinetic determination in H4[α-SiW12O40] electrolyte media.",
keywords = "electrode heterogeneity, electron transfer kinetics, Fe process, Fourier transformed alternating current voltammetry, medium effect",
author = "Mingyue Lin and Jiezhen Li and Dawei Pan and Bond, {Alan M} and Jie Zhang",
year = "2017",
month = "9",
day = "20",
doi = "10.1016/j.electacta.2017.07.155",
language = "English",
volume = "249",
pages = "421--430",
journal = "Electrochimica Acta",
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A Systematic Study of the Mass Transport, Kinetic and Thermodynamic Properties of the FeIII/II Process at Glassy Carbon and Boron-Doped Diamond Electrodes. / Lin, Mingyue; Li, Jiezhen; Pan, Dawei; Bond, Alan M; Zhang, Jie.

In: Electrochimica Acta, Vol. 249, 20.09.2017, p. 421-430.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - A Systematic Study of the Mass Transport, Kinetic and Thermodynamic Properties of the FeIII/II Process at Glassy Carbon and Boron-Doped Diamond Electrodes

AU - Lin, Mingyue

AU - Li, Jiezhen

AU - Pan, Dawei

AU - Bond, Alan M

AU - Zhang, Jie

PY - 2017/9/20

Y1 - 2017/9/20

N2 - The heterogeneous electron transfer kinetics (k0 values), mass transport and thermodynamic properties (E0 values) associated with the FeIII/II process have been determined in aqueous solutions containing 0.1 M HCl, HClO4, bis(trifluoromethanesulfonyl)imide (HNTf2) or 0.05 M silicotungstic acid (H4[α-SiW12O40]) supporting electrolytes. The diffusion coefficient (D) values for FeIII and FeII are dependent on the radius of the electrolyte anion and follow the order D(SiW12O40 4−) < D(NTf2 −) < D(ClO4 −) < D(Cl−). The k0 values are found to be smaller at boron doped diamond (BDD) electrodes than glassy carbon (GC) electrodes, and influenced by the ion-pairing between electrolyte anions and FeIII and FeII. Based on the formal potential value, HNTf2 is found to be a more innocent electrolyte than commonly used HClO4 with regard to determine the true k0 values of the outer-sphere [Fe(H2O)6]3+/2+ process. Fourier transformed large amplitude alternating current voltammetry, which provides favorable signal to background ratio, was used to determine k0 values associated with the FeIII/II process in H4[α-SiW12O40] and HNTf2 electrolyte media at GC electrodes and probe the implications of the heterogeneity of the BDD electrode surface on the electrode kinetic determination in H4[α-SiW12O40] electrolyte media.

AB - The heterogeneous electron transfer kinetics (k0 values), mass transport and thermodynamic properties (E0 values) associated with the FeIII/II process have been determined in aqueous solutions containing 0.1 M HCl, HClO4, bis(trifluoromethanesulfonyl)imide (HNTf2) or 0.05 M silicotungstic acid (H4[α-SiW12O40]) supporting electrolytes. The diffusion coefficient (D) values for FeIII and FeII are dependent on the radius of the electrolyte anion and follow the order D(SiW12O40 4−) < D(NTf2 −) < D(ClO4 −) < D(Cl−). The k0 values are found to be smaller at boron doped diamond (BDD) electrodes than glassy carbon (GC) electrodes, and influenced by the ion-pairing between electrolyte anions and FeIII and FeII. Based on the formal potential value, HNTf2 is found to be a more innocent electrolyte than commonly used HClO4 with regard to determine the true k0 values of the outer-sphere [Fe(H2O)6]3+/2+ process. Fourier transformed large amplitude alternating current voltammetry, which provides favorable signal to background ratio, was used to determine k0 values associated with the FeIII/II process in H4[α-SiW12O40] and HNTf2 electrolyte media at GC electrodes and probe the implications of the heterogeneity of the BDD electrode surface on the electrode kinetic determination in H4[α-SiW12O40] electrolyte media.

KW - electrode heterogeneity

KW - electron transfer kinetics

KW - Fe process

KW - Fourier transformed alternating current voltammetry

KW - medium effect

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U2 - 10.1016/j.electacta.2017.07.155

DO - 10.1016/j.electacta.2017.07.155

M3 - Article

VL - 249

SP - 421

EP - 430

JO - Electrochimica Acta

JF - Electrochimica Acta

SN - 0013-4686

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