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

doi:10.1016/j.cattod.2012.04.022

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

Chemistry

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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 language	English
Pages (from-to)	79-86
Number of pages	8
Journal	Catalysis Today
Volume	202
Early online date	21 Jun 2012
DOIs	https://doi.org/10.1016/j.cattod.2012.04.022
Publication status	Published - 15 Mar 2013

Bibliographical 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.

Keywords

Au
formic acid
ATR-SEIRAS
electroxidation
direct path
absorbed formate

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© 2012. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
Accepted author manuscript, 758 KBLicence: CC BY-NC-ND

Cite this

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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 = mar,

day = "15",

doi = "10.1016/j.cattod.2012.04.022",

language = "English",

volume = "202",

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journal = "Catalysis Today",

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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

SN - 0920-5861

VL - 202

SP - 79

EP - 86

JO - Catalysis Today

JF - Catalysis Today

ER -

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

Abstract

Bibliographical note

Keywords

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