TEMPO/viologen electrochemical heterojunction for diffusion-controlled redox mediation: a highly rectifying bilayer-sandwiched device based on cross-reaction at the interface between dissimilar redox polymers.
Identifieur interne : 000031 ( Main/Exploration ); précédent : 000030; suivant : 000032TEMPO/viologen electrochemical heterojunction for diffusion-controlled redox mediation: a highly rectifying bilayer-sandwiched device based on cross-reaction at the interface between dissimilar redox polymers.
Auteurs : RBID : pubmed:24559298Abstract
A couple of totally reversible redox-active molecules, which are different in redox potentials, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and viologen (V(2+)), were employed to give rise to a rectified redox conduction effect. Single-layer and bilayer devices were fabricated using polymers containing these sites as pendant groups per repeating unit. The devices were obtained by sandwiching the redox polymer layer(s) with indium tin oxide (ITO)/glass and Pt foil electrodes. Electrochemical measurements of the single-layer device composed of polynorbornene-bearing TEMPO (PTNB) exhibited a diffusion-limited current-voltage response based on the TEMPO(+)/TEMPO exchange reaction, which was almost equivalent to a redox gradient through the PTNB layer depending upon the thickness. The bilayer device gave rise to the current rectification because of the thermodynamically favored cross-reaction between TEMPO(+) and V(+) at the polymer/polymer interface. A current-voltage response obtained for the bilayer device demonstrated a two-step diffusion-limited current behavior as a result of the concurrent V(2+)/V(+) and V(+)/V(0) exchange reactions according to the voltage and suggested that the charge transport process through the device was most likely to be rate-determined by a redox gradient in the polymer layer. Current collection experiments revealed a charge transport balance throughout the device, as a result of the electrochemical stability and robustness of the polymers in both redox states.
DOI: 10.1021/am405527y
PubMed: 24559298
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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">TEMPO/viologen electrochemical heterojunction for diffusion-controlled redox mediation: a highly rectifying bilayer-sandwiched device based on cross-reaction at the interface between dissimilar redox polymers.</title><author><name sortKey="Tokue, Hiroshi" uniqKey="Tokue H">Hiroshi Tokue</name><affiliation wicri:level="1"><nlm:affiliation>Department of Applied Chemistry, Waseda University , Tokyo 169-8555, Japan.</nlm:affiliation><country xml:lang="fr">Japon</country><wicri:regionArea>Department of Applied Chemistry, Waseda University , Tokyo 169-8555</wicri:regionArea></affiliation></author><author><name sortKey="Oyaizu, Kenichi" uniqKey="Oyaizu K">Kenichi Oyaizu</name></author><author><name sortKey="Sukegawa, Takashi" uniqKey="Sukegawa T">Takashi Sukegawa</name></author><author><name sortKey="Nishide, Hiroyuki" uniqKey="Nishide H">Hiroyuki Nishide</name></author></titleStmt><publicationStmt><date when="2014">2014</date><idno type="doi">10.1021/am405527y</idno><idno type="RBID">pubmed:24559298</idno><idno type="pmid">24559298</idno><idno type="wicri:Area/Main/Corpus">000146</idno><idno type="wicri:Area/Main/Curation">000146</idno><idno type="wicri:Area/Main/Exploration">000031</idno></publicationStmt></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">A couple of totally reversible redox-active molecules, which are different in redox potentials, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and viologen (V(2+)), were employed to give rise to a rectified redox conduction effect. Single-layer and bilayer devices were fabricated using polymers containing these sites as pendant groups per repeating unit. The devices were obtained by sandwiching the redox polymer layer(s) with indium tin oxide (ITO)/glass and Pt foil electrodes. Electrochemical measurements of the single-layer device composed of polynorbornene-bearing TEMPO (PTNB) exhibited a diffusion-limited current-voltage response based on the TEMPO(+)/TEMPO exchange reaction, which was almost equivalent to a redox gradient through the PTNB layer depending upon the thickness. The bilayer device gave rise to the current rectification because of the thermodynamically favored cross-reaction between TEMPO(+) and V(+) at the polymer/polymer interface. A current-voltage response obtained for the bilayer device demonstrated a two-step diffusion-limited current behavior as a result of the concurrent V(2+)/V(+) and V(+)/V(0) exchange reactions according to the voltage and suggested that the charge transport process through the device was most likely to be rate-determined by a redox gradient in the polymer layer. Current collection experiments revealed a charge transport balance throughout the device, as a result of the electrochemical stability and robustness of the polymers in both redox states.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="In-Process"><PMID Version="1">24559298</PMID><DateCreated><Year>2014</Year><Month>03</Month><Day>26</Day></DateCreated><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1944-8252</ISSN><JournalIssue CitedMedium="Internet"><Volume>6</Volume><Issue>6</Issue><PubDate><Year>2014</Year><Month>Mar</Month><Day>26</Day></PubDate></JournalIssue><Title>ACS applied materials & interfaces</Title><ISOAbbreviation>ACS Appl Mater Interfaces</ISOAbbreviation></Journal><ArticleTitle>TEMPO/viologen electrochemical heterojunction for diffusion-controlled redox mediation: a highly rectifying bilayer-sandwiched device based on cross-reaction at the interface between dissimilar redox polymers.</ArticleTitle><Pagination><MedlinePgn>4043-9</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1021/am405527y</ELocationID><Abstract><AbstractText>A couple of totally reversible redox-active molecules, which are different in redox potentials, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and viologen (V(2+)), were employed to give rise to a rectified redox conduction effect. Single-layer and bilayer devices were fabricated using polymers containing these sites as pendant groups per repeating unit. The devices were obtained by sandwiching the redox polymer layer(s) with indium tin oxide (ITO)/glass and Pt foil electrodes. Electrochemical measurements of the single-layer device composed of polynorbornene-bearing TEMPO (PTNB) exhibited a diffusion-limited current-voltage response based on the TEMPO(+)/TEMPO exchange reaction, which was almost equivalent to a redox gradient through the PTNB layer depending upon the thickness. The bilayer device gave rise to the current rectification because of the thermodynamically favored cross-reaction between TEMPO(+) and V(+) at the polymer/polymer interface. A current-voltage response obtained for the bilayer device demonstrated a two-step diffusion-limited current behavior as a result of the concurrent V(2+)/V(+) and V(+)/V(0) exchange reactions according to the voltage and suggested that the charge transport process through the device was most likely to be rate-determined by a redox gradient in the polymer layer. Current collection experiments revealed a charge transport balance throughout the device, as a result of the electrochemical stability and robustness of the polymers in both redox states.</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Tokue</LastName><ForeName>Hiroshi</ForeName><Initials>H</Initials><Affiliation>Department of Applied Chemistry, Waseda University , Tokyo 169-8555, Japan.</Affiliation></Author><Author ValidYN="Y"><LastName>Oyaizu</LastName><ForeName>Kenichi</ForeName><Initials>K</Initials></Author><Author ValidYN="Y"><LastName>Sukegawa</LastName><ForeName>Takashi</ForeName><Initials>T</Initials></Author><Author ValidYN="Y"><LastName>Nishide</LastName><ForeName>Hiroyuki</ForeName><Initials>H</Initials></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType>Journal Article</PublicationType><PublicationType>Research Support, Non-U.S. Gov't</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2014</Year><Month>03</Month><Day>04</Day></ArticleDate></Article><MedlineJournalInfo><Country>United States</Country><MedlineTA>ACS Appl Mater Interfaces</MedlineTA><NlmUniqueID>101504991</NlmUniqueID><ISSNLinking>1944-8244</ISSNLinking></MedlineJournalInfo><CitationSubset>IM</CitationSubset></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="aheadofprint"><Year>2014</Year><Month>3</Month><Day>4</Day></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2014</Year><Month>2</Month><Day>25</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2014</Year><Month>2</Month><Day>25</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2014</Year><Month>2</Month><Day>25</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="doi">10.1021/am405527y</ArticleId><ArticleId IdType="pubmed">24559298</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
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