Cyclic versus staircase voltammetry in electrocatalysis: Theoretical aspects

Bin Hai, Yuriy V. Tolmachev, Kenneth A. Loparo, Claudio Zanelli, Daniel Alberto Scherson

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The transient response of a series RC equivalent circuit to a staircase potential perturbation, where R represents the resistance due to the electrolyte and C a voltage dependent interfacial capacitance, has been examined theoretically using, as a model system, capacitance data believed to be characteristic of the Pt (111) 0.1 M HCl O4 interface. Solutions to the governing algebraic differential equation were obtained by numerical techniques, which were then used to generate current versus potential curves assuming various data sampling protocols. In general, the resulting curves were not only found to be sensitive to the time at which the current was sampled within each step, but, also, quite different than those obtained by scanning the potential at a constant rate, as in conventional linear scan voltammetry (LSV). Excellent agreement between the staircase voltammetry (SCV) and LSV results could be achieved, however, based on values of the average step currents, Q step /T, where Qstep represents the total charge injected during the step and T the length of the step, as well as by the postfiltering technique introduced by He [Anal. Chem., 67, 986 (1995)]. Implications of these results for studies involving electrocatalytic systems are discussed.

Original languageEnglish
JournalJournal of the Electrochemical Society
Volume158
Issue number2
DOIs
Publication statusPublished - 2011 Jan 5
Externally publishedYes

Fingerprint

Electrocatalysis
stairways
Voltammetry
Capacitance
Transient analysis
Equivalent circuits
Electrolytes
capacitance
RC circuits
data sampling
Differential equations
Sampling
Scanning
transient response
curves
equivalent circuits
Electric potential
differential equations
electrolytes
perturbation

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Renewable Energy, Sustainability and the Environment
  • Condensed Matter Physics
  • Surfaces, Coatings and Films
  • Electrochemistry
  • Materials Chemistry

Cite this

Cyclic versus staircase voltammetry in electrocatalysis : Theoretical aspects. / Hai, Bin; Tolmachev, Yuriy V.; Loparo, Kenneth A.; Zanelli, Claudio; Scherson, Daniel Alberto.

In: Journal of the Electrochemical Society, Vol. 158, No. 2, 05.01.2011.

Research output: Contribution to journalArticle

Hai, Bin ; Tolmachev, Yuriy V. ; Loparo, Kenneth A. ; Zanelli, Claudio ; Scherson, Daniel Alberto. / Cyclic versus staircase voltammetry in electrocatalysis : Theoretical aspects. In: Journal of the Electrochemical Society. 2011 ; Vol. 158, No. 2.
@article{7736cffcfc684f968d8abd04e59b6226,
title = "Cyclic versus staircase voltammetry in electrocatalysis: Theoretical aspects",
abstract = "The transient response of a series RC equivalent circuit to a staircase potential perturbation, where R represents the resistance due to the electrolyte and C a voltage dependent interfacial capacitance, has been examined theoretically using, as a model system, capacitance data believed to be characteristic of the Pt (111) 0.1 M HCl O4 interface. Solutions to the governing algebraic differential equation were obtained by numerical techniques, which were then used to generate current versus potential curves assuming various data sampling protocols. In general, the resulting curves were not only found to be sensitive to the time at which the current was sampled within each step, but, also, quite different than those obtained by scanning the potential at a constant rate, as in conventional linear scan voltammetry (LSV). Excellent agreement between the staircase voltammetry (SCV) and LSV results could be achieved, however, based on values of the average step currents, Q step /T, where Qstep represents the total charge injected during the step and T the length of the step, as well as by the postfiltering technique introduced by He [Anal. Chem., 67, 986 (1995)]. Implications of these results for studies involving electrocatalytic systems are discussed.",
author = "Bin Hai and Tolmachev, {Yuriy V.} and Loparo, {Kenneth A.} and Claudio Zanelli and Scherson, {Daniel Alberto}",
year = "2011",
month = "1",
day = "5",
doi = "10.1149/1.3512914",
language = "English",
volume = "158",
journal = "Journal of the Electrochemical Society",
issn = "0013-4651",
publisher = "Electrochemical Society, Inc.",
number = "2",

}

TY - JOUR

T1 - Cyclic versus staircase voltammetry in electrocatalysis

T2 - Theoretical aspects

AU - Hai, Bin

AU - Tolmachev, Yuriy V.

AU - Loparo, Kenneth A.

AU - Zanelli, Claudio

AU - Scherson, Daniel Alberto

PY - 2011/1/5

Y1 - 2011/1/5

N2 - The transient response of a series RC equivalent circuit to a staircase potential perturbation, where R represents the resistance due to the electrolyte and C a voltage dependent interfacial capacitance, has been examined theoretically using, as a model system, capacitance data believed to be characteristic of the Pt (111) 0.1 M HCl O4 interface. Solutions to the governing algebraic differential equation were obtained by numerical techniques, which were then used to generate current versus potential curves assuming various data sampling protocols. In general, the resulting curves were not only found to be sensitive to the time at which the current was sampled within each step, but, also, quite different than those obtained by scanning the potential at a constant rate, as in conventional linear scan voltammetry (LSV). Excellent agreement between the staircase voltammetry (SCV) and LSV results could be achieved, however, based on values of the average step currents, Q step /T, where Qstep represents the total charge injected during the step and T the length of the step, as well as by the postfiltering technique introduced by He [Anal. Chem., 67, 986 (1995)]. Implications of these results for studies involving electrocatalytic systems are discussed.

AB - The transient response of a series RC equivalent circuit to a staircase potential perturbation, where R represents the resistance due to the electrolyte and C a voltage dependent interfacial capacitance, has been examined theoretically using, as a model system, capacitance data believed to be characteristic of the Pt (111) 0.1 M HCl O4 interface. Solutions to the governing algebraic differential equation were obtained by numerical techniques, which were then used to generate current versus potential curves assuming various data sampling protocols. In general, the resulting curves were not only found to be sensitive to the time at which the current was sampled within each step, but, also, quite different than those obtained by scanning the potential at a constant rate, as in conventional linear scan voltammetry (LSV). Excellent agreement between the staircase voltammetry (SCV) and LSV results could be achieved, however, based on values of the average step currents, Q step /T, where Qstep represents the total charge injected during the step and T the length of the step, as well as by the postfiltering technique introduced by He [Anal. Chem., 67, 986 (1995)]. Implications of these results for studies involving electrocatalytic systems are discussed.

UR - http://www.scopus.com/inward/record.url?scp=78650749274&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=78650749274&partnerID=8YFLogxK

U2 - 10.1149/1.3512914

DO - 10.1149/1.3512914

M3 - Article

AN - SCOPUS:78650749274

VL - 158

JO - Journal of the Electrochemical Society

JF - Journal of the Electrochemical Society

SN - 0013-4651

IS - 2

ER -