Towards direct electroanalysis in seawater: understanding the role of the buffer capacity of seawater in proton-coupled electron transfer reactions
The study of electrochemical reactions in seawater requires understanding of the associated coupled chemistry with the components of seawater, especially the role of the carbonate-bicarbonate buffer system in the case of proton coupled electron transfer reactions. We report the comparative paradigma...
Published in: | The Journal of Physical Chemistry C |
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Main Authors: | , , , |
Format: | Article in Journal/Newspaper |
Language: | English |
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American Chemical Society
2021
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Online Access: | https://doi.org/10.1021/acs.jpcc.1c09142 https://ora.ox.ac.uk/objects/uuid:2ee1e15e-06b1-4eeb-99d2-14826a19d945 |
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ftuloxford:oai:ora.ox.ac.uk:uuid:2ee1e15e-06b1-4eeb-99d2-14826a19d945 2023-05-15T15:52:44+02:00 Towards direct electroanalysis in seawater: understanding the role of the buffer capacity of seawater in proton-coupled electron transfer reactions Pindar, R Batchelor-McAuley, C Yang, M Compton, R 2021-12-06 https://doi.org/10.1021/acs.jpcc.1c09142 https://ora.ox.ac.uk/objects/uuid:2ee1e15e-06b1-4eeb-99d2-14826a19d945 eng eng American Chemical Society doi:10.1021/acs.jpcc.1c09142 https://ora.ox.ac.uk/objects/uuid:2ee1e15e-06b1-4eeb-99d2-14826a19d945 https://doi.org/10.1021/acs.jpcc.1c09142 info:eu-repo/semantics/openAccess Journal article 2021 ftuloxford https://doi.org/10.1021/acs.jpcc.1c09142 2022-12-22T23:06:07Z The study of electrochemical reactions in seawater requires understanding of the associated coupled chemistry with the components of seawater, especially the role of the carbonate-bicarbonate buffer system in the case of proton coupled electron transfer reactions. We report the comparative paradigmatic voltammetric response of the reversible hydrogen oxidation reaction (HOR) in the absence or presence of dibasic phosphate, formate or bicarbonate. Electrochemically and chemically reversible voltammetry is seen in aqueous 0.7 M NaCl at platinum macro-electrodes in the absence of a buffer whilst the presence of a chemically stable buffer systems, such as phosphate or formate, leads either to a cathodic shift in the oxidation potential for high buffer concentrations or to a split wave for concentrations approximately a factor of two less than the dissolved H2. In the case of bicarbonate buffer the dehydration of carbonic acid on the voltammetric timescale leads to chemically irreversible voltammetric behaviour, with a similar response measured in authentic seawater. Numerical simulations based on a simple Nernstian model with literature values for kinetic and thermodynamic parameters are reported which display excellent agreement with experiment. Article in Journal/Newspaper Carbonic acid ORA - Oxford University Research Archive The Journal of Physical Chemistry C 125 51 27949 27958 |
institution |
Open Polar |
collection |
ORA - Oxford University Research Archive |
op_collection_id |
ftuloxford |
language |
English |
description |
The study of electrochemical reactions in seawater requires understanding of the associated coupled chemistry with the components of seawater, especially the role of the carbonate-bicarbonate buffer system in the case of proton coupled electron transfer reactions. We report the comparative paradigmatic voltammetric response of the reversible hydrogen oxidation reaction (HOR) in the absence or presence of dibasic phosphate, formate or bicarbonate. Electrochemically and chemically reversible voltammetry is seen in aqueous 0.7 M NaCl at platinum macro-electrodes in the absence of a buffer whilst the presence of a chemically stable buffer systems, such as phosphate or formate, leads either to a cathodic shift in the oxidation potential for high buffer concentrations or to a split wave for concentrations approximately a factor of two less than the dissolved H2. In the case of bicarbonate buffer the dehydration of carbonic acid on the voltammetric timescale leads to chemically irreversible voltammetric behaviour, with a similar response measured in authentic seawater. Numerical simulations based on a simple Nernstian model with literature values for kinetic and thermodynamic parameters are reported which display excellent agreement with experiment. |
format |
Article in Journal/Newspaper |
author |
Pindar, R Batchelor-McAuley, C Yang, M Compton, R |
spellingShingle |
Pindar, R Batchelor-McAuley, C Yang, M Compton, R Towards direct electroanalysis in seawater: understanding the role of the buffer capacity of seawater in proton-coupled electron transfer reactions |
author_facet |
Pindar, R Batchelor-McAuley, C Yang, M Compton, R |
author_sort |
Pindar, R |
title |
Towards direct electroanalysis in seawater: understanding the role of the buffer capacity of seawater in proton-coupled electron transfer reactions |
title_short |
Towards direct electroanalysis in seawater: understanding the role of the buffer capacity of seawater in proton-coupled electron transfer reactions |
title_full |
Towards direct electroanalysis in seawater: understanding the role of the buffer capacity of seawater in proton-coupled electron transfer reactions |
title_fullStr |
Towards direct electroanalysis in seawater: understanding the role of the buffer capacity of seawater in proton-coupled electron transfer reactions |
title_full_unstemmed |
Towards direct electroanalysis in seawater: understanding the role of the buffer capacity of seawater in proton-coupled electron transfer reactions |
title_sort |
towards direct electroanalysis in seawater: understanding the role of the buffer capacity of seawater in proton-coupled electron transfer reactions |
publisher |
American Chemical Society |
publishDate |
2021 |
url |
https://doi.org/10.1021/acs.jpcc.1c09142 https://ora.ox.ac.uk/objects/uuid:2ee1e15e-06b1-4eeb-99d2-14826a19d945 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_relation |
doi:10.1021/acs.jpcc.1c09142 https://ora.ox.ac.uk/objects/uuid:2ee1e15e-06b1-4eeb-99d2-14826a19d945 https://doi.org/10.1021/acs.jpcc.1c09142 |
op_rights |
info:eu-repo/semantics/openAccess |
op_doi |
https://doi.org/10.1021/acs.jpcc.1c09142 |
container_title |
The Journal of Physical Chemistry C |
container_volume |
125 |
container_issue |
51 |
container_start_page |
27949 |
op_container_end_page |
27958 |
_version_ |
1766387839956680704 |