Metallocene Voltammetric Reference Related to a Normal Hydrogen
Electrode

J 2025

Metallocene Voltammetric Reference Related to a Normal Hydrogen Electrode

DORCAK, Vlastimil; Jan HRBÁČ; Jiri JANATA a Jan VACEK

Základní údaje

Originální název

Metallocene Voltammetric Reference Related to a Normal Hydrogen Electrode

Autoři

DORCAK, Vlastimil (703 Slovensko); Jan HRBÁČ (203 Česká republika, domácí); Jiri JANATA (840 Spojené státy) a Jan VACEK (203 Česká republika, garant)

Vydání

Journal of Physical Chemistry Letters, Washington DC, American Chemical Society, 2025, 1948-7185

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10405 Electrochemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 4.600 v roce 2024

Organizační jednotka

Přírodovědecká fakulta

DOI

https://doi.org/10.1021/acs.jpclett.4c03390

UT WoS

001435159500001

EID Scopus

2-s2.0-86000144343

Klíčová slova anglicky

ferrocene; oxidation; solvents; films

Štítky

rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 15. 7. 2025 09:25, Mgr. Marie Novosadová Šípková, DiS.

Anotace

V originále

The potentials of electrochemical processes in ideal aqueous media are related to the potential of a normal hydrogen electrode (NHE). However, in non-ideal media, the potentials of a metallocene redox couple are used as a reference. Such measurements with free metallocene in solution are complicated by adsorption and mass transport phenomena and solvation effects. Herein, a platinum electrode with an anchored ferrocene moiety (Pt,Fc) was used for cyclic voltammetric measurements of the potential of ferrocene/ferrocenium (Fc/Fc+) redox transformation in not only non-aqueous but, for the first time, aqueous solutions as well. This enabled us to eliminate the aforementioned problems associated with the application of free metallocene molecules in solution and, thus, to relate the midpoint potential (E pm) of the Fc/Fc+ redox couple to a NHE. After elimination of the liquid junction potential in an aqueous 0.1 M KCl solution at 25 degrees C, the average intraday E pm value obtained with freshly prepared Pt,Fc electrodes was found to be 0.312 +/- 0.008 V versus the secondary Ag|AgCl electrode. The Pt,Fc electrode can be applied for the standardization of electrochemical measurements and investigation of solvation phenomena at interfaces in non-ideal media.

Citovat

DORCAK, Vlastimil; Jan HRBÁČ; Jiri JANATA a Jan VACEK. Metallocene Voltammetric Reference Related to a Normal Hydrogen Electrode. Journal of Physical Chemistry Letters. Washington DC: American Chemical Society, 2025, roč. 16, č. 10, s. 2487-2491. ISSN 1948-7185. Dostupné z: https://doi.org/10.1021/acs.jpclett.4c03390.

@article{2483279,
   author = {Dorcak, Vlastimil and Hrbáč, Jan and Janata, Jiri and Vacek, Jan},
   article_location = {Washington DC},
   article_number = {10},
   doi = {https://doi.org/10.1021/acs.jpclett.4c03390},
   keywords = {ferrocene; oxidation; solvents; films},
   language = {eng},
   issn = {1948-7185},
   journal = {Journal of Physical Chemistry Letters},
   title = {Metallocene Voltammetric Reference Related to a Normal Hydrogen Electrode},
   url = {https://pubs.acs.org/doi/10.1021/acs.jpclett.4c03390},
   volume = {16},
   year = {2025}
}

TY  - JOUR
ID  - 2483279
AU  - Dorcak, Vlastimil - Hrbáč, Jan - Janata, Jiri - Vacek, Jan
PY  - 2025
TI  - Metallocene Voltammetric Reference Related to a Normal Hydrogen Electrode
JF  - Journal of Physical Chemistry Letters
VL  - 16
IS  - 10
SP  - 2487-2491
EP  - 2487-2491
PB  - American Chemical Society
SN  - 19487185
KW  - ferrocene
KW  - oxidation
KW  - solvents
KW  - films
UR  - https://pubs.acs.org/doi/10.1021/acs.jpclett.4c03390
N2  - The potentials of electrochemical processes in ideal aqueous media are related to the potential of a normal hydrogen electrode (NHE). However, in non-ideal media, the potentials of a metallocene redox couple are used as a reference. Such measurements with free metallocene in solution are complicated by adsorption and mass transport phenomena and solvation effects. Herein, a platinum electrode with an anchored ferrocene moiety (Pt,Fc) was used for cyclic voltammetric measurements of the potential of ferrocene/ferrocenium (Fc/Fc+) redox transformation in not only non-aqueous but, for the first time, aqueous solutions as well. This enabled us to eliminate the aforementioned problems associated with the application of free metallocene molecules in solution and, thus, to relate the midpoint potential (E pm) of the Fc/Fc+ redox couple to a NHE. After elimination of the liquid junction potential in an aqueous 0.1 M KCl solution at 25 degrees C, the average intraday E pm value obtained with freshly prepared Pt,Fc electrodes was found to be 0.312 +/- 0.008 V versus the secondary Ag|AgCl electrode. The Pt,Fc electrode can be applied for the standardization of electrochemical measurements and investigation of solvation phenomena at interfaces in non-ideal media.
ER  -

DORCAK, Vlastimil; Jan HRBÁČ; Jiri JANATA a Jan VACEK. Metallocene Voltammetric Reference Related to a Normal Hydrogen Electrode. \textit{Journal of Physical Chemistry Letters}. Washington DC: American Chemical Society, 2025, roč.~16, č.~10, s.~2487-2491. ISSN~1948-7185. Dostupné z: https://doi.org/10.1021/acs.jpclett.4c03390.

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