Effect of the substituent of the cation of N-octylpyridinium hexafluorophosphate in the electrical and electrochemical response of carbon paste electrodes modified with these ionic liquids

Francesca Fuenzalida, Daniel Aravena, Camilo García, Macarena García, Roxana Arce, Galo Ramírez, Carlos Díaz, Mauricio Isaacs, María del Carmen Arévalo, María J. Aguirre

Resultado de la investigación: Article

3 Citas (Scopus)

Resumen

A series of N-octylpyridinium hexafluorophosphate ionic liquids (ILs), ascribed as ROpyPF6, where Opy = N-octylpyridinium and R are the substituents –OCH3, –CH3, –CF3 and –CN at the para position of the cation, were characterized and employed as binders in carbon paste electrodes (CILEs) to evaluate the electron donating or withdrawing effects of the substituent of the cation in physical and electrochemical properties of these CILEs. Substituents strongly affect the melting point of the ILs, the electric properties of the CILEs measured by electrochemical impedance spectroscopy, and the electrochemical behavior measured by the response for an outer-sphere reaction (ferro/ferricyanide redox couple) and for an inner-sphere irreversible reaction (oxidation of sulfite). Results show that ILs can be separated in two different groups: those that have withdrawing electron substituents and those that have donating-electron substituents. OpyPF6 has a behavior similar to those that have withdrawing electron substituents. Carbon paste electrode prepared with mineral oil as binder (CPE) has a very different behavior and is described for comparison purposes only. Results show that the ILs with withdrawing electron substituents have more polarized cations (a more localized positive charge) acquiring a slight ionic character in comparison to the ILs with donating substituents. The electron withdrawing effect modifies the hydrogen-fluorine interactions and also the electrostatic interactions between anion and cation, modifying the electric and electrochemical response of the CILEs, resulting in more conductive and homogeneous surfaces.

Idioma originalEnglish
Páginas (desde-hasta)959-969
Número de páginas11
PublicaciónElectrochimica Acta
Volumen258
DOI
EstadoPublished - 20 dic 2017

Huella dactilar

Ionic Liquids
Ointments
Ionic liquids
Cations
Carbon
Positive ions
Electrodes
Electrons
Adhesive pastes
Binders
Mineral Oil
Sulfites
Fluorine
Mineral oils
Coulomb interactions
Electrochemical impedance spectroscopy
Electrochemical properties
Anions
Melting point
Hydrogen

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Electrochemistry

Citar esto

Fuenzalida, Francesca ; Aravena, Daniel ; García, Camilo ; García, Macarena ; Arce, Roxana ; Ramírez, Galo ; Díaz, Carlos ; Isaacs, Mauricio ; Arévalo, María del Carmen ; Aguirre, María J. / Effect of the substituent of the cation of N-octylpyridinium hexafluorophosphate in the electrical and electrochemical response of carbon paste electrodes modified with these ionic liquids. En: Electrochimica Acta. 2017 ; Vol. 258. pp. 959-969.
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title = "Effect of the substituent of the cation of N-octylpyridinium hexafluorophosphate in the electrical and electrochemical response of carbon paste electrodes modified with these ionic liquids",
abstract = "A series of N-octylpyridinium hexafluorophosphate ionic liquids (ILs), ascribed as ROpyPF6, where Opy = N-octylpyridinium and R are the substituents –OCH3, –CH3, –CF3 and –CN at the para position of the cation, were characterized and employed as binders in carbon paste electrodes (CILEs) to evaluate the electron donating or withdrawing effects of the substituent of the cation in physical and electrochemical properties of these CILEs. Substituents strongly affect the melting point of the ILs, the electric properties of the CILEs measured by electrochemical impedance spectroscopy, and the electrochemical behavior measured by the response for an outer-sphere reaction (ferro/ferricyanide redox couple) and for an inner-sphere irreversible reaction (oxidation of sulfite). Results show that ILs can be separated in two different groups: those that have withdrawing electron substituents and those that have donating-electron substituents. OpyPF6 has a behavior similar to those that have withdrawing electron substituents. Carbon paste electrode prepared with mineral oil as binder (CPE) has a very different behavior and is described for comparison purposes only. Results show that the ILs with withdrawing electron substituents have more polarized cations (a more localized positive charge) acquiring a slight ionic character in comparison to the ILs with donating substituents. The electron withdrawing effect modifies the hydrogen-fluorine interactions and also the electrostatic interactions between anion and cation, modifying the electric and electrochemical response of the CILEs, resulting in more conductive and homogeneous surfaces.",
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author = "Francesca Fuenzalida and Daniel Aravena and Camilo Garc{\'i}a and Macarena Garc{\'i}a and Roxana Arce and Galo Ram{\'i}rez and Carlos D{\'i}az and Mauricio Isaacs and Ar{\'e}valo, {Mar{\'i}a del Carmen} and Aguirre, {Mar{\'i}a J.}",
year = "2017",
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pages = "959--969",
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Effect of the substituent of the cation of N-octylpyridinium hexafluorophosphate in the electrical and electrochemical response of carbon paste electrodes modified with these ionic liquids. / Fuenzalida, Francesca; Aravena, Daniel; García, Camilo; García, Macarena; Arce, Roxana; Ramírez, Galo; Díaz, Carlos; Isaacs, Mauricio; Arévalo, María del Carmen; Aguirre, María J.

En: Electrochimica Acta, Vol. 258, 20.12.2017, p. 959-969.

Resultado de la investigación: Article

TY - JOUR

T1 - Effect of the substituent of the cation of N-octylpyridinium hexafluorophosphate in the electrical and electrochemical response of carbon paste electrodes modified with these ionic liquids

AU - Fuenzalida, Francesca

AU - Aravena, Daniel

AU - García, Camilo

AU - García, Macarena

AU - Arce, Roxana

AU - Ramírez, Galo

AU - Díaz, Carlos

AU - Isaacs, Mauricio

AU - Arévalo, María del Carmen

AU - Aguirre, María J.

PY - 2017/12/20

Y1 - 2017/12/20

N2 - A series of N-octylpyridinium hexafluorophosphate ionic liquids (ILs), ascribed as ROpyPF6, where Opy = N-octylpyridinium and R are the substituents –OCH3, –CH3, –CF3 and –CN at the para position of the cation, were characterized and employed as binders in carbon paste electrodes (CILEs) to evaluate the electron donating or withdrawing effects of the substituent of the cation in physical and electrochemical properties of these CILEs. Substituents strongly affect the melting point of the ILs, the electric properties of the CILEs measured by electrochemical impedance spectroscopy, and the electrochemical behavior measured by the response for an outer-sphere reaction (ferro/ferricyanide redox couple) and for an inner-sphere irreversible reaction (oxidation of sulfite). Results show that ILs can be separated in two different groups: those that have withdrawing electron substituents and those that have donating-electron substituents. OpyPF6 has a behavior similar to those that have withdrawing electron substituents. Carbon paste electrode prepared with mineral oil as binder (CPE) has a very different behavior and is described for comparison purposes only. Results show that the ILs with withdrawing electron substituents have more polarized cations (a more localized positive charge) acquiring a slight ionic character in comparison to the ILs with donating substituents. The electron withdrawing effect modifies the hydrogen-fluorine interactions and also the electrostatic interactions between anion and cation, modifying the electric and electrochemical response of the CILEs, resulting in more conductive and homogeneous surfaces.

AB - A series of N-octylpyridinium hexafluorophosphate ionic liquids (ILs), ascribed as ROpyPF6, where Opy = N-octylpyridinium and R are the substituents –OCH3, –CH3, –CF3 and –CN at the para position of the cation, were characterized and employed as binders in carbon paste electrodes (CILEs) to evaluate the electron donating or withdrawing effects of the substituent of the cation in physical and electrochemical properties of these CILEs. Substituents strongly affect the melting point of the ILs, the electric properties of the CILEs measured by electrochemical impedance spectroscopy, and the electrochemical behavior measured by the response for an outer-sphere reaction (ferro/ferricyanide redox couple) and for an inner-sphere irreversible reaction (oxidation of sulfite). Results show that ILs can be separated in two different groups: those that have withdrawing electron substituents and those that have donating-electron substituents. OpyPF6 has a behavior similar to those that have withdrawing electron substituents. Carbon paste electrode prepared with mineral oil as binder (CPE) has a very different behavior and is described for comparison purposes only. Results show that the ILs with withdrawing electron substituents have more polarized cations (a more localized positive charge) acquiring a slight ionic character in comparison to the ILs with donating substituents. The electron withdrawing effect modifies the hydrogen-fluorine interactions and also the electrostatic interactions between anion and cation, modifying the electric and electrochemical response of the CILEs, resulting in more conductive and homogeneous surfaces.

KW - Carbon paste electrode

KW - Carbon paste-ionic liquid electrode

KW - N-octylpyridinium hexafluorophosphate

KW - Substituent effect

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U2 - 10.1016/j.electacta.2017.11.147

DO - 10.1016/j.electacta.2017.11.147

M3 - Article

VL - 258

SP - 959

EP - 969

JO - Electrochimica Acta

JF - Electrochimica Acta

SN - 0013-4686

ER -