Performance assessment of a polymer electrolyte membrane electrochemical reactor under alkaline conditions - a case study with the electrooxidation of alcohols

A novel polymer electrolyte membrane electrochemical reactor (PEMER) configuration has been employed for the direct electrooxidation of propargyl alcohol (PGA), a model primary alcohol, towards its carboxylic acid derivatives in alkaline medium. The PEMER configuration comprised of an anode and cath...

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Autores: García Cruz, Leticia, Casado Coterillo, Clara|||0000-0002-4454-7652, Irabien Gulías, Ángel|||0000-0002-2411-4163, Montiel Leguey, Vicente, Iniesta Valcárcel, Jesús
Formato: artículo
Fecha de publicación:2016
País:España
Recursos:Universidad de Cantabria (UC)
Repositorio:UCrea Repositorio Abierto de la Universidad de Cantabria
Idioma:inglés
OAI Identifier:oai:repositorio.unican.es:10902/11177
Acesso em linha:http://hdl.handle.net/10902/11177
Access Level:acceso abierto
Palavra-chave:Polymer Electrolyte Membrane Electrochemical Reactor (PEMER) configuration
Anionic alkaline exchange membrane
Anionic ionomer
Chitosan/Poly(vinyl) alcohol membrane
Alcohol electrooxidation
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spelling Performance assessment of a polymer electrolyte membrane electrochemical reactor under alkaline conditions - a case study with the electrooxidation of alcoholsOn the performance of a polymer electrolyte membrane electrochemical reactor for electrosynthesis of carboxylic acids in alkaline mediaGarcía Cruz, LeticiaCasado Coterillo, Clara|||0000-0002-4454-7652Irabien Gulías, Ángel|||0000-0002-2411-4163Montiel Leguey, VicenteIniesta Valcárcel, JesúsPolymer Electrolyte Membrane Electrochemical Reactor (PEMER) configurationAnionic alkaline exchange membraneAnionic ionomerChitosan/Poly(vinyl) alcohol membraneAlcohol electrooxidationA novel polymer electrolyte membrane electrochemical reactor (PEMER) configuration has been employed for the direct electrooxidation of propargyl alcohol (PGA), a model primary alcohol, towards its carboxylic acid derivatives in alkaline medium. The PEMER configuration comprised of an anode and cathode based on nanoparticulate Ni and Pt electrocatalysts, respectively, supported on carbonaceous substrates. The electrooxidation of PGA was performed in 1.0 M NaOH, where a cathode based on a gas diffusion electrode was manufactured for the reduction of oxygen in alkaline conditions. The performance of a novel alkaline anion-exchange membrane based on Chitosan (CS) and Poly(vinyl) alcohol (PVA) in a 50:50 composition ratio doped with a 5 wt.% of poly (4-vinylpyridine) organic ionomer cross-linked, methyl chloride quaternary salt resin (4VP) was assessed as solid polymer electrolyte. The influence of 4VP anionic ionomer loading of 7, 12 and 20 wt.% incorporated into the electrocatalytic layers was examined by SEM and cyclic voltammetry (CV) upon the optimisation of the electroactive area, the mechanical stability and cohesion of the catalytic ink onto the carbonaceous substrate for both electrodes. The performance of the 4VP/CS:PVA membrane was compared with the commercial alkaline anion-exchange membrane FAA -a membrane generally used in direct alcohol alkaline fuel cells- in terms of polarisation plots in alkaline conditions. Furthermore, preparative electrolyses of the electrooxidation of PGA was performed under alkaline conditions of 1 M NaOH at constant current density of 20 mA cm-2 using a PEMER configuration to provide proof of the principle of the feasibility of the electrooxidation of other alcohols in alkaline media. PGA conversion to Z isomers of 3-(2-propynoxy)-2-propenoic acid (Z-PPA) was circa 0.77, with average current efficiency of 0.32. Alkaline stability of the membranes within the PEMER configuration was finally evaluated after the electrooxidation of PGA.This work has been funded by the Spanish MINECO through grants CTQ2013-48280-C3-3-R, at the University of Alicante, and CTQ2012-31229 and RYC2011-08550, at the University of Cantabria. L.G.C. for her PhD fellowship BES-2011-045147 at the University of Alicante and the EEBB-14-09094 mobility grant for a research stay at the University of Cantabria. The authors gratefully thank Dr. José Solla Gullón for his advice on the synthesis of platinum nanoparticles, from the Institute of Electrochemistry at the University of Alicante.ElsevierUniversidad de Cantabria20162016-07-10journal articlehttp://purl.org/coar/resource_type/c_6501NAhttp://purl.org/coar/version/c_be7fb7dd8ff6fe43info:eu-repo/semantics/articlehttp://hdl.handle.net/10902/11177Electrochimica Acta, 2016, 206, 165-175reponame:UCrea Repositorio Abierto de la Universidad de Cantabriainstname:Universidad de Cantabria (UC)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Atribución-NoComercial-SinDerivadas 3.0 Españahttp://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccessoai:repositorio.unican.es:10902/111772026-06-02T12:39:31Z
dc.title.none.fl_str_mv Performance assessment of a polymer electrolyte membrane electrochemical reactor under alkaline conditions - a case study with the electrooxidation of alcohols
On the performance of a polymer electrolyte membrane electrochemical reactor for electrosynthesis of carboxylic acids in alkaline media
title Performance assessment of a polymer electrolyte membrane electrochemical reactor under alkaline conditions - a case study with the electrooxidation of alcohols
spellingShingle Performance assessment of a polymer electrolyte membrane electrochemical reactor under alkaline conditions - a case study with the electrooxidation of alcohols
García Cruz, Leticia
Polymer Electrolyte Membrane Electrochemical Reactor (PEMER) configuration
Anionic alkaline exchange membrane
Anionic ionomer
Chitosan/Poly(vinyl) alcohol membrane
Alcohol electrooxidation
title_short Performance assessment of a polymer electrolyte membrane electrochemical reactor under alkaline conditions - a case study with the electrooxidation of alcohols
title_full Performance assessment of a polymer electrolyte membrane electrochemical reactor under alkaline conditions - a case study with the electrooxidation of alcohols
title_fullStr Performance assessment of a polymer electrolyte membrane electrochemical reactor under alkaline conditions - a case study with the electrooxidation of alcohols
title_full_unstemmed Performance assessment of a polymer electrolyte membrane electrochemical reactor under alkaline conditions - a case study with the electrooxidation of alcohols
title_sort Performance assessment of a polymer electrolyte membrane electrochemical reactor under alkaline conditions - a case study with the electrooxidation of alcohols
dc.creator.none.fl_str_mv García Cruz, Leticia
Casado Coterillo, Clara|||0000-0002-4454-7652
Irabien Gulías, Ángel|||0000-0002-2411-4163
Montiel Leguey, Vicente
Iniesta Valcárcel, Jesús
author García Cruz, Leticia
author_facet García Cruz, Leticia
Casado Coterillo, Clara|||0000-0002-4454-7652
Irabien Gulías, Ángel|||0000-0002-2411-4163
Montiel Leguey, Vicente
Iniesta Valcárcel, Jesús
author_role author
author2 Casado Coterillo, Clara|||0000-0002-4454-7652
Irabien Gulías, Ángel|||0000-0002-2411-4163
Montiel Leguey, Vicente
Iniesta Valcárcel, Jesús
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Universidad de Cantabria
dc.subject.none.fl_str_mv Polymer Electrolyte Membrane Electrochemical Reactor (PEMER) configuration
Anionic alkaline exchange membrane
Anionic ionomer
Chitosan/Poly(vinyl) alcohol membrane
Alcohol electrooxidation
topic Polymer Electrolyte Membrane Electrochemical Reactor (PEMER) configuration
Anionic alkaline exchange membrane
Anionic ionomer
Chitosan/Poly(vinyl) alcohol membrane
Alcohol electrooxidation
description A novel polymer electrolyte membrane electrochemical reactor (PEMER) configuration has been employed for the direct electrooxidation of propargyl alcohol (PGA), a model primary alcohol, towards its carboxylic acid derivatives in alkaline medium. The PEMER configuration comprised of an anode and cathode based on nanoparticulate Ni and Pt electrocatalysts, respectively, supported on carbonaceous substrates. The electrooxidation of PGA was performed in 1.0 M NaOH, where a cathode based on a gas diffusion electrode was manufactured for the reduction of oxygen in alkaline conditions. The performance of a novel alkaline anion-exchange membrane based on Chitosan (CS) and Poly(vinyl) alcohol (PVA) in a 50:50 composition ratio doped with a 5 wt.% of poly (4-vinylpyridine) organic ionomer cross-linked, methyl chloride quaternary salt resin (4VP) was assessed as solid polymer electrolyte. The influence of 4VP anionic ionomer loading of 7, 12 and 20 wt.% incorporated into the electrocatalytic layers was examined by SEM and cyclic voltammetry (CV) upon the optimisation of the electroactive area, the mechanical stability and cohesion of the catalytic ink onto the carbonaceous substrate for both electrodes. The performance of the 4VP/CS:PVA membrane was compared with the commercial alkaline anion-exchange membrane FAA -a membrane generally used in direct alcohol alkaline fuel cells- in terms of polarisation plots in alkaline conditions. Furthermore, preparative electrolyses of the electrooxidation of PGA was performed under alkaline conditions of 1 M NaOH at constant current density of 20 mA cm-2 using a PEMER configuration to provide proof of the principle of the feasibility of the electrooxidation of other alcohols in alkaline media. PGA conversion to Z isomers of 3-(2-propynoxy)-2-propenoic acid (Z-PPA) was circa 0.77, with average current efficiency of 0.32. Alkaline stability of the membranes within the PEMER configuration was finally evaluated after the electrooxidation of PGA.
publishDate 2016
dc.date.none.fl_str_mv 2016
2016-07-10
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
NA
http://purl.org/coar/version/c_be7fb7dd8ff6fe43
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10902/11177
url http://hdl.handle.net/10902/11177
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Atribución-NoComercial-SinDerivadas 3.0 España
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Atribución-NoComercial-SinDerivadas 3.0 España
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv Electrochimica Acta, 2016, 206, 165-175
reponame:UCrea Repositorio Abierto de la Universidad de Cantabria
instname:Universidad de Cantabria (UC)
instname_str Universidad de Cantabria (UC)
reponame_str UCrea Repositorio Abierto de la Universidad de Cantabria
collection UCrea Repositorio Abierto de la Universidad de Cantabria
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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