Tracking oxygen atoms in electrochemical CO oxidation – Part I: :Oxygen exchange via CO2 hydration
We report a new method to measure the kinetic rate constant of CO 2 hydration using electrochemical oxidation of carbon monoxide (CO oxidation) in isotope-labeled electrolyte. CO oxidation is often used as a model reaction to investigate the surface of metallic electrocatalysts, most notably in CO s...
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ftdtupubl:oai:pure.atira.dk:publications/bc531bd6-dd31-40a5-b427-f0d7b1dd6fba 2024-09-15T18:01:39+00:00 Tracking oxygen atoms in electrochemical CO oxidation – Part I: :Oxygen exchange via CO2 hydration Scott, Søren B. Kibsgaard, Jakob Vesborg, Peter C.K. Chorkendorff, Ib 2021 application/pdf https://orbit.dtu.dk/en/publications/bc531bd6-dd31-40a5-b427-f0d7b1dd6fba https://doi.org/10.1016/j.electacta.2021.137842 https://backend.orbit.dtu.dk/ws/files/240712608/COox_I_H2CO3_revised.pdf eng eng https://orbit.dtu.dk/en/publications/bc531bd6-dd31-40a5-b427-f0d7b1dd6fba info:eu-repo/semantics/openAccess Scott , S B , Kibsgaard , J , Vesborg , P C K & Chorkendorff , I 2021 , ' Tracking oxygen atoms in electrochemical CO oxidation – Part I: : Oxygen exchange via CO2 hydration ' , Electrochimica Acta , vol. 374 , 137842 . https://doi.org/10.1016/j.electacta.2021.137842 Kinetics CO2 hydration CO oxidation DEMS Mechanisms article 2021 ftdtupubl https://doi.org/10.1016/j.electacta.2021.137842 2024-08-13T00:03:06Z We report a new method to measure the kinetic rate constant of CO 2 hydration using electrochemical oxidation of carbon monoxide (CO oxidation) in isotope-labeled electrolyte. CO oxidation is often used as a model reaction to investigate the surface of metallic electrocatalysts, most notably in CO stripping experiments. Using chip-based electrochemistry mass spectrometry with 18 O-labeled electrolyte we show that: 1) For CO stripping experiments on Pt, one oxygen in the product CO 2 comes from the reactant CO and the other comes from the electrolyte, consistent with the Langmuir-Hinshelwood mechanism involving the adsorbates ∗CO and ∗OH. 2) Some of the formed CO 2 subsequently exchanges oxygen with the electrolyte via short-lived carbonic acid. We use the time-dependent isotopic ratios to calculate the kinetic reaction rate constant of the CO 2 hydration reaction and compare it to literature. By doing this at two different temperatures we show that the method is robust and that 18 O-labeled CO stripping experiments provide an accurate measurement of the rate constant for CO 2 hydration. Chip-based electrochemistry mass spectrometry combined with isotopic labeling is thus shown to be a versatile and powerful tool for elucidating mechanistic aspects of homogeneous reactions as well as electrocatalytic reactions. Article in Journal/Newspaper Carbonic acid Technical University of Denmark: DTU Orbit Electrochimica Acta 374 137842 |
institution |
Open Polar |
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Technical University of Denmark: DTU Orbit |
op_collection_id |
ftdtupubl |
language |
English |
topic |
Kinetics CO2 hydration CO oxidation DEMS Mechanisms |
spellingShingle |
Kinetics CO2 hydration CO oxidation DEMS Mechanisms Scott, Søren B. Kibsgaard, Jakob Vesborg, Peter C.K. Chorkendorff, Ib Tracking oxygen atoms in electrochemical CO oxidation – Part I: :Oxygen exchange via CO2 hydration |
topic_facet |
Kinetics CO2 hydration CO oxidation DEMS Mechanisms |
description |
We report a new method to measure the kinetic rate constant of CO 2 hydration using electrochemical oxidation of carbon monoxide (CO oxidation) in isotope-labeled electrolyte. CO oxidation is often used as a model reaction to investigate the surface of metallic electrocatalysts, most notably in CO stripping experiments. Using chip-based electrochemistry mass spectrometry with 18 O-labeled electrolyte we show that: 1) For CO stripping experiments on Pt, one oxygen in the product CO 2 comes from the reactant CO and the other comes from the electrolyte, consistent with the Langmuir-Hinshelwood mechanism involving the adsorbates ∗CO and ∗OH. 2) Some of the formed CO 2 subsequently exchanges oxygen with the electrolyte via short-lived carbonic acid. We use the time-dependent isotopic ratios to calculate the kinetic reaction rate constant of the CO 2 hydration reaction and compare it to literature. By doing this at two different temperatures we show that the method is robust and that 18 O-labeled CO stripping experiments provide an accurate measurement of the rate constant for CO 2 hydration. Chip-based electrochemistry mass spectrometry combined with isotopic labeling is thus shown to be a versatile and powerful tool for elucidating mechanistic aspects of homogeneous reactions as well as electrocatalytic reactions. |
format |
Article in Journal/Newspaper |
author |
Scott, Søren B. Kibsgaard, Jakob Vesborg, Peter C.K. Chorkendorff, Ib |
author_facet |
Scott, Søren B. Kibsgaard, Jakob Vesborg, Peter C.K. Chorkendorff, Ib |
author_sort |
Scott, Søren B. |
title |
Tracking oxygen atoms in electrochemical CO oxidation – Part I: :Oxygen exchange via CO2 hydration |
title_short |
Tracking oxygen atoms in electrochemical CO oxidation – Part I: :Oxygen exchange via CO2 hydration |
title_full |
Tracking oxygen atoms in electrochemical CO oxidation – Part I: :Oxygen exchange via CO2 hydration |
title_fullStr |
Tracking oxygen atoms in electrochemical CO oxidation – Part I: :Oxygen exchange via CO2 hydration |
title_full_unstemmed |
Tracking oxygen atoms in electrochemical CO oxidation – Part I: :Oxygen exchange via CO2 hydration |
title_sort |
tracking oxygen atoms in electrochemical co oxidation – part i: :oxygen exchange via co2 hydration |
publishDate |
2021 |
url |
https://orbit.dtu.dk/en/publications/bc531bd6-dd31-40a5-b427-f0d7b1dd6fba https://doi.org/10.1016/j.electacta.2021.137842 https://backend.orbit.dtu.dk/ws/files/240712608/COox_I_H2CO3_revised.pdf |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Scott , S B , Kibsgaard , J , Vesborg , P C K & Chorkendorff , I 2021 , ' Tracking oxygen atoms in electrochemical CO oxidation – Part I: : Oxygen exchange via CO2 hydration ' , Electrochimica Acta , vol. 374 , 137842 . https://doi.org/10.1016/j.electacta.2021.137842 |
op_relation |
https://orbit.dtu.dk/en/publications/bc531bd6-dd31-40a5-b427-f0d7b1dd6fba |
op_rights |
info:eu-repo/semantics/openAccess |
op_doi |
https://doi.org/10.1016/j.electacta.2021.137842 |
container_title |
Electrochimica Acta |
container_volume |
374 |
container_start_page |
137842 |
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1810438756828708864 |