Electrooxidation of formic acid on gold: An ATR-SEIRAS study of the role of adsorbed formate

Angel Cuesta, Gema Cabello, Fabian W. Hartl, Maria Escudero-Escribano, Cristina Vaz-Dominguez, Ludwig A. Kibler, Masatoshi Osawa, Claudio Gutierrez

Research output: Contribution to journalArticle

40 Citations (Scopus)
5 Downloads (Pure)

Abstract

Formate was found to be the only adsorbed species detected with time-resolved ATR-SEIRAS during the electrooxidation of formic acid on Au in acidic media. No adsorbed CO was detected, since even in CO-saturated acidic solutions the adsorption of CO on gold is negligible. The onset of formic acid electrooxidation coincides with that of formate electroadsorption, pointing to bridge-bonded adsorbed formate as the reaction intermediate. Furthermore, at constant potential the current increases quadratically with the formate coverage, which indicates that the rate-determining step in the oxidation of adsorbed formate to CO2 is a bimolecular reaction between adjacent formate species. The rate of this reaction was unaffected by potential changes, which unequivocally confirms its chemical character.
Original languageEnglish
Pages (from-to)79-86
Number of pages8
JournalCatalysis Today
Volume202
Early online date21 Jun 2012
DOIs
Publication statusPublished - 15 Mar 2013

Fingerprint

formic acid
Electrooxidation
Formic acid
Gold
Reaction intermediates
Carbon Monoxide
Adsorption
Oxidation

Keywords

  • Au
  • formic acid
  • ATR-SEIRAS
  • electroxidation
  • direct path
  • absorbed formate

Cite this

Cuesta, A., Cabello, G., Hartl, F. W., Escudero-Escribano, M., Vaz-Dominguez, C., Kibler, L. A., ... Gutierrez, C. (2013). Electrooxidation of formic acid on gold: An ATR-SEIRAS study of the role of adsorbed formate. Catalysis Today, 202, 79-86. https://doi.org/10.1016/j.cattod.2012.04.022

Electrooxidation of formic acid on gold : An ATR-SEIRAS study of the role of adsorbed formate. / Cuesta, Angel; Cabello, Gema; Hartl, Fabian W.; Escudero-Escribano, Maria; Vaz-Dominguez, Cristina; Kibler, Ludwig A. ; Osawa, Masatoshi; Gutierrez, Claudio.

In: Catalysis Today, Vol. 202, 15.03.2013, p. 79-86.

Research output: Contribution to journalArticle

Cuesta, A, Cabello, G, Hartl, FW, Escudero-Escribano, M, Vaz-Dominguez, C, Kibler, LA, Osawa, M & Gutierrez, C 2013, 'Electrooxidation of formic acid on gold: An ATR-SEIRAS study of the role of adsorbed formate', Catalysis Today, vol. 202, pp. 79-86. https://doi.org/10.1016/j.cattod.2012.04.022
Cuesta A, Cabello G, Hartl FW, Escudero-Escribano M, Vaz-Dominguez C, Kibler LA et al. Electrooxidation of formic acid on gold: An ATR-SEIRAS study of the role of adsorbed formate. Catalysis Today. 2013 Mar 15;202:79-86. https://doi.org/10.1016/j.cattod.2012.04.022
Cuesta, Angel ; Cabello, Gema ; Hartl, Fabian W. ; Escudero-Escribano, Maria ; Vaz-Dominguez, Cristina ; Kibler, Ludwig A. ; Osawa, Masatoshi ; Gutierrez, Claudio. / Electrooxidation of formic acid on gold : An ATR-SEIRAS study of the role of adsorbed formate. In: Catalysis Today. 2013 ; Vol. 202. pp. 79-86.
@article{8e0ef2149cab4986a7fe7d6fed2602bb,
title = "Electrooxidation of formic acid on gold: An ATR-SEIRAS study of the role of adsorbed formate",
abstract = "Formate was found to be the only adsorbed species detected with time-resolved ATR-SEIRAS during the electrooxidation of formic acid on Au in acidic media. No adsorbed CO was detected, since even in CO-saturated acidic solutions the adsorption of CO on gold is negligible. The onset of formic acid electrooxidation coincides with that of formate electroadsorption, pointing to bridge-bonded adsorbed formate as the reaction intermediate. Furthermore, at constant potential the current increases quadratically with the formate coverage, which indicates that the rate-determining step in the oxidation of adsorbed formate to CO2 is a bimolecular reaction between adjacent formate species. The rate of this reaction was unaffected by potential changes, which unequivocally confirms its chemical character.",
keywords = "Au, formic acid, ATR-SEIRAS, electroxidation, direct path, absorbed formate",
author = "Angel Cuesta and Gema Cabello and Hartl, {Fabian W.} and Maria Escudero-Escribano and Cristina Vaz-Dominguez and Kibler, {Ludwig A.} and Masatoshi Osawa and Claudio Gutierrez",
note = "Funding from the DGI (Spanish Ministry of Education and Science) through Projects CTQ2009-07017 and PLE2009-0008 is gratefully acknowledged. M.E.-E. acknowledges an FPI fellowship from the Spanish Ministry of Science and Innovation and an accommodation grant at the Residencia de Estudiantes from the Madrid City Council. C. V.-D. acknowledges a JAE-Doc fellowship from CSIC.",
year = "2013",
month = "3",
day = "15",
doi = "10.1016/j.cattod.2012.04.022",
language = "English",
volume = "202",
pages = "79--86",
journal = "Catalysis Today",
issn = "0920-5861",
publisher = "Elsevier",

}

TY - JOUR

T1 - Electrooxidation of formic acid on gold

T2 - An ATR-SEIRAS study of the role of adsorbed formate

AU - Cuesta, Angel

AU - Cabello, Gema

AU - Hartl, Fabian W.

AU - Escudero-Escribano, Maria

AU - Vaz-Dominguez, Cristina

AU - Kibler, Ludwig A.

AU - Osawa, Masatoshi

AU - Gutierrez, Claudio

N1 - Funding from the DGI (Spanish Ministry of Education and Science) through Projects CTQ2009-07017 and PLE2009-0008 is gratefully acknowledged. M.E.-E. acknowledges an FPI fellowship from the Spanish Ministry of Science and Innovation and an accommodation grant at the Residencia de Estudiantes from the Madrid City Council. C. V.-D. acknowledges a JAE-Doc fellowship from CSIC.

PY - 2013/3/15

Y1 - 2013/3/15

N2 - Formate was found to be the only adsorbed species detected with time-resolved ATR-SEIRAS during the electrooxidation of formic acid on Au in acidic media. No adsorbed CO was detected, since even in CO-saturated acidic solutions the adsorption of CO on gold is negligible. The onset of formic acid electrooxidation coincides with that of formate electroadsorption, pointing to bridge-bonded adsorbed formate as the reaction intermediate. Furthermore, at constant potential the current increases quadratically with the formate coverage, which indicates that the rate-determining step in the oxidation of adsorbed formate to CO2 is a bimolecular reaction between adjacent formate species. The rate of this reaction was unaffected by potential changes, which unequivocally confirms its chemical character.

AB - Formate was found to be the only adsorbed species detected with time-resolved ATR-SEIRAS during the electrooxidation of formic acid on Au in acidic media. No adsorbed CO was detected, since even in CO-saturated acidic solutions the adsorption of CO on gold is negligible. The onset of formic acid electrooxidation coincides with that of formate electroadsorption, pointing to bridge-bonded adsorbed formate as the reaction intermediate. Furthermore, at constant potential the current increases quadratically with the formate coverage, which indicates that the rate-determining step in the oxidation of adsorbed formate to CO2 is a bimolecular reaction between adjacent formate species. The rate of this reaction was unaffected by potential changes, which unequivocally confirms its chemical character.

KW - Au

KW - formic acid

KW - ATR-SEIRAS

KW - electroxidation

KW - direct path

KW - absorbed formate

U2 - 10.1016/j.cattod.2012.04.022

DO - 10.1016/j.cattod.2012.04.022

M3 - Article

VL - 202

SP - 79

EP - 86

JO - Catalysis Today

JF - Catalysis Today

SN - 0920-5861

ER -