A neutron reflectivity study of [Os(bipy)2(PVP)10Cl]+ polymer film modified electrodes: effect of redox state and counter ion
Identifieur interne : 002184 ( Istex/Corpus ); précédent : 002183; suivant : 002185A neutron reflectivity study of [Os(bipy)2(PVP)10Cl]+ polymer film modified electrodes: effect of redox state and counter ion
Auteurs : Robert W. Wilson ; Robert Cubitt ; Andrew Glidle ; A. Robert Hillman ; Paul M. Saville ; Johannes G. VosSource :
- Electrochimica Acta [ 0013-4686 ] ; 1999.
English descriptors
- KwdEn :
- Acmw, Acta, Anion, Chem, Counter ions, Critical edge, Cyclic, Cyclic voltammograms, Cycling, Electrochemical, Electrochemical responses, Electrochimica, Electrochimica acta, Electrode, Electrolyte, Elsevier science, Gold layer, Interface, Interference fringes, Length densities, Length density, Neutron, Neutron data, Neutron experiment, Nmol, Open circuit, Outer layer, Overall electroneutrality, Oxidation state, Oxidation states, Oxidized, Oxidized state, Perchlorate, Perchlorate media, Perchlorate solution, Perchlorate solutions, Polymer, Polymer structure, Polymer volume fraction, Positive step, Ptsa, Qcmw, Quartz, Redox, Redox cycling, Redox state, Solution contrasts, Solvent, Solvent content, Solvent penetration, Spatial distribution, Surface coverage.
- Teeft :
- Acmw, Acta, Anion, Chem, Counter ions, Critical edge, Cyclic, Cyclic voltammograms, Cycling, Electrochemical, Electrochemical responses, Electrochimica, Electrochimica acta, Electrode, Electrolyte, Elsevier science, Gold layer, Interface, Interference fringes, Length densities, Length density, Neutron, Neutron data, Neutron experiment, Nmol, Open circuit, Outer layer, Overall electroneutrality, Oxidation state, Oxidation states, Oxidized, Oxidized state, Perchlorate, Perchlorate media, Perchlorate solution, Perchlorate solutions, Polymer, Polymer structure, Polymer volume fraction, Positive step, Ptsa, Qcmw, Quartz, Redox, Redox cycling, Redox state, Solution contrasts, Solvent, Solvent content, Solvent penetration, Spatial distribution, Surface coverage.
Abstract
Abstract: The effects of redox state (Os[II] vs. Os[III]) and counter ion (perchlorate vs. p-toluenesulphonate) on the polymer and solvent density distributions in films of electroactive [Os(bipy)2(PVP)10Cl]+ were determined using neutron reflectivity. The changes in polymer structure upon immersion in solvent and upon redox cycling the film in these electrolytes were also investigated. The as-prepared dry polymer film swelled appreciably upon immersion in aqueous solutions. Using p-toluenesulphonate as the counter ion caused pronounced changes to film structure upon both redox cycling and holding it in a fixed oxidation state; the perchlorate anion was found to be much less disruptive. Surprisingly, the effect on film structure of changing anion was much more pronounced than the effect of changing film redox state, i.e. charge density.
Url:
DOI: 10.1016/S0013-4686(99)00113-9
Links to Exploration step
ISTEX:B230E935257F716377AA95E118DD935BDC3CE307Le document en format XML
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Wilson</name><affiliation><mods:affiliation>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Cubitt, Robert" sort="Cubitt, Robert" uniqKey="Cubitt R" first="Robert" last="Cubitt">Robert Cubitt</name><affiliation><mods:affiliation>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Glidle, Andrew" sort="Glidle, Andrew" uniqKey="Glidle A" first="Andrew" last="Glidle">Andrew Glidle</name><affiliation><mods:affiliation>Bioelectronics, Glasgow University, Glasgow G12 8QQ, UK</mods:affiliation></affiliation></author><author><name sortKey="Hillman, A Robert" sort="Hillman, A Robert" uniqKey="Hillman A" first="A. Robert" last="Hillman">A. 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Wilson</name><affiliation><mods:affiliation>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Cubitt, Robert" sort="Cubitt, Robert" uniqKey="Cubitt R" first="Robert" last="Cubitt">Robert Cubitt</name><affiliation><mods:affiliation>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Glidle, Andrew" sort="Glidle, Andrew" uniqKey="Glidle A" first="Andrew" last="Glidle">Andrew Glidle</name><affiliation><mods:affiliation>Bioelectronics, Glasgow University, Glasgow G12 8QQ, UK</mods:affiliation></affiliation></author><author><name sortKey="Hillman, A Robert" sort="Hillman, A Robert" uniqKey="Hillman A" first="A. Robert" last="Hillman">A. Robert Hillman</name><affiliation><mods:affiliation>E-mail: arh7@le.ac.uk</mods:affiliation></affiliation><affiliation><mods:affiliation>Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK</mods:affiliation></affiliation></author><author><name sortKey="Saville, Paul M" sort="Saville, Paul M" uniqKey="Saville P" first="Paul M" last="Saville">Paul M. Saville</name><affiliation><mods:affiliation>Research School of Chemistry, The Australian National University, Canberra 0200, Australia</mods:affiliation></affiliation></author><author><name sortKey="Vos, Johannes G" sort="Vos, Johannes G" uniqKey="Vos J" first="Johannes G" last="Vos">Johannes G. Vos</name><affiliation><mods:affiliation>School of Chemical Sciences, Dublin City University, Dublin 9, Ireland</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Electrochimica Acta</title><title level="j" type="abbrev">EA</title><idno type="ISSN">0013-4686</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1999">1999</date><biblScope unit="volume">44</biblScope><biblScope unit="issue">20</biblScope><biblScope unit="page" from="3533">3533</biblScope><biblScope unit="page" to="3548">3548</biblScope></imprint><idno type="ISSN">0013-4686</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0013-4686</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Acmw</term><term>Acta</term><term>Anion</term><term>Chem</term><term>Counter ions</term><term>Critical edge</term><term>Cyclic</term><term>Cyclic voltammograms</term><term>Cycling</term><term>Electrochemical</term><term>Electrochemical responses</term><term>Electrochimica</term><term>Electrochimica acta</term><term>Electrode</term><term>Electrolyte</term><term>Elsevier science</term><term>Gold layer</term><term>Interface</term><term>Interference fringes</term><term>Length densities</term><term>Length density</term><term>Neutron</term><term>Neutron data</term><term>Neutron experiment</term><term>Nmol</term><term>Open circuit</term><term>Outer layer</term><term>Overall electroneutrality</term><term>Oxidation state</term><term>Oxidation states</term><term>Oxidized</term><term>Oxidized state</term><term>Perchlorate</term><term>Perchlorate media</term><term>Perchlorate solution</term><term>Perchlorate solutions</term><term>Polymer</term><term>Polymer structure</term><term>Polymer volume fraction</term><term>Positive step</term><term>Ptsa</term><term>Qcmw</term><term>Quartz</term><term>Redox</term><term>Redox cycling</term><term>Redox state</term><term>Solution contrasts</term><term>Solvent</term><term>Solvent content</term><term>Solvent penetration</term><term>Spatial distribution</term><term>Surface coverage</term></keywords><keywords scheme="Teeft" xml:lang="en"><term>Acmw</term><term>Acta</term><term>Anion</term><term>Chem</term><term>Counter ions</term><term>Critical edge</term><term>Cyclic</term><term>Cyclic voltammograms</term><term>Cycling</term><term>Electrochemical</term><term>Electrochemical responses</term><term>Electrochimica</term><term>Electrochimica acta</term><term>Electrode</term><term>Electrolyte</term><term>Elsevier science</term><term>Gold layer</term><term>Interface</term><term>Interference fringes</term><term>Length densities</term><term>Length density</term><term>Neutron</term><term>Neutron data</term><term>Neutron experiment</term><term>Nmol</term><term>Open circuit</term><term>Outer layer</term><term>Overall electroneutrality</term><term>Oxidation state</term><term>Oxidation states</term><term>Oxidized</term><term>Oxidized state</term><term>Perchlorate</term><term>Perchlorate media</term><term>Perchlorate solution</term><term>Perchlorate solutions</term><term>Polymer</term><term>Polymer structure</term><term>Polymer volume fraction</term><term>Positive step</term><term>Ptsa</term><term>Qcmw</term><term>Quartz</term><term>Redox</term><term>Redox cycling</term><term>Redox state</term><term>Solution contrasts</term><term>Solvent</term><term>Solvent content</term><term>Solvent penetration</term><term>Spatial distribution</term><term>Surface coverage</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Abstract: The effects of redox state (Os[II] vs. Os[III]) and counter ion (perchlorate vs. p-toluenesulphonate) on the polymer and solvent density distributions in films of electroactive [Os(bipy)2(PVP)10Cl]+ were determined using neutron reflectivity. The changes in polymer structure upon immersion in solvent and upon redox cycling the film in these electrolytes were also investigated. The as-prepared dry polymer film swelled appreciably upon immersion in aqueous solutions. Using p-toluenesulphonate as the counter ion caused pronounced changes to film structure upon both redox cycling and holding it in a fixed oxidation state; the perchlorate anion was found to be much less disruptive. Surprisingly, the effect on film structure of changing anion was much more pronounced than the effect of changing film redox state, i.e. charge density.</div></front></TEI><istex><corpusName>elsevier</corpusName><keywords><teeft><json:string>redox</json:string><json:string>polymer</json:string><json:string>length density</json:string><json:string>cycling</json:string><json:string>redox cycling</json:string><json:string>ptsa</json:string><json:string>neutron</json:string><json:string>perchlorate</json:string><json:string>oxidized</json:string><json:string>acta</json:string><json:string>electrochimica acta</json:string><json:string>electrochimica</json:string><json:string>qcmw</json:string><json:string>electrolyte</json:string><json:string>acmw</json:string><json:string>cyclic</json:string><json:string>electrochemical</json:string><json:string>redox state</json:string><json:string>oxidation state</json:string><json:string>oxidized state</json:string><json:string>chem</json:string><json:string>nmol</json:string><json:string>outer layer</json:string><json:string>surface coverage</json:string><json:string>counter ions</json:string><json:string>critical edge</json:string><json:string>polymer volume fraction</json:string><json:string>neutron data</json:string><json:string>open circuit</json:string><json:string>solution contrasts</json:string><json:string>solvent penetration</json:string><json:string>interference fringes</json:string><json:string>cyclic voltammograms</json:string><json:string>polymer structure</json:string><json:string>solvent</json:string><json:string>quartz</json:string><json:string>anion</json:string><json:string>electrode</json:string><json:string>oxidation states</json:string><json:string>neutron experiment</json:string><json:string>elsevier science</json:string><json:string>length densities</json:string><json:string>positive step</json:string><json:string>perchlorate solution</json:string><json:string>gold layer</json:string><json:string>spatial distribution</json:string><json:string>perchlorate solutions</json:string><json:string>solvent content</json:string><json:string>electrochemical responses</json:string><json:string>perchlorate media</json:string><json:string>overall electroneutrality</json:string><json:string>interface</json:string></teeft></keywords><author><json:item><name>Robert W Wilson</name><affiliations><json:string>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</json:string></affiliations></json:item><json:item><name>Robert Cubitt</name><affiliations><json:string>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</json:string></affiliations></json:item><json:item><name>Andrew Glidle</name><affiliations><json:string>Bioelectronics, Glasgow University, Glasgow G12 8QQ, UK</json:string></affiliations></json:item><json:item><name>A.Robert Hillman</name><affiliations><json:string>E-mail: arh7@le.ac.uk</json:string><json:string>Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK</json:string></affiliations></json:item><json:item><name>Paul M Saville</name><affiliations><json:string>Research School of Chemistry, The Australian National University, Canberra 0200, Australia</json:string></affiliations></json:item><json:item><name>Johannes G Vos</name><affiliations><json:string>School of Chemical Sciences, Dublin City University, Dublin 9, Ireland</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>Redox polymer</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Modified electrode</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Neutron reflectivity</value></json:item></subject><arkIstex>ark:/67375/6H6-7NHCSNMF-V</arkIstex><language><json:string>eng</json:string></language><originalGenre><json:string>Full-length article</json:string></originalGenre><abstract>Abstract: The effects of redox state (Os[II] vs. Os[III]) and counter ion (perchlorate vs. p-toluenesulphonate) on the polymer and solvent density distributions in films of electroactive [Os(bipy)2(PVP)10Cl]+ were determined using neutron reflectivity. The changes in polymer structure upon immersion in solvent and upon redox cycling the film in these electrolytes were also investigated. The as-prepared dry polymer film swelled appreciably upon immersion in aqueous solutions. Using p-toluenesulphonate as the counter ion caused pronounced changes to film structure upon both redox cycling and holding it in a fixed oxidation state; the perchlorate anion was found to be much less disruptive. Surprisingly, the effect on film structure of changing anion was much more pronounced than the effect of changing film redox state, i.e. charge density.</abstract><qualityIndicators><refBibsNative>true</refBibsNative><abstractWordCount>123</abstractWordCount><abstractCharCount>848</abstractCharCount><keywordCount>3</keywordCount><score>8.476</score><pdfWordCount>7350</pdfWordCount><pdfCharCount>44312</pdfCharCount><pdfVersion>1.2</pdfVersion><pdfPageCount>16</pdfPageCount><pdfPageSize>543 x 745 pts</pdfPageSize></qualityIndicators><title>A neutron reflectivity study of [Os(bipy)2(PVP)10Cl]+ polymer film modified electrodes: effect of redox state and counter ion</title><pii><json:string>S0013-4686(99)00113-9</json:string></pii><genre><json:string>research-article</json:string></genre><host><title>Electrochimica Acta</title><language><json:string>unknown</json:string></language><publicationDate>1999</publicationDate><issn><json:string>0013-4686</json:string></issn><pii><json:string>S0013-4686(00)X0080-1</json:string></pii><volume>44</volume><issue>20</issue><pages><first>3533</first><last>3548</last></pages><genre><json:string>journal</json:string></genre></host><namedEntities><unitex><date><json:string>3545</json:string><json:string>1999</json:string><json:string>3536</json:string></date><geogName></geogName><orgName><json:string>Research School of Chemistry, The Australian National University, Canberra</json:string><json:string>Dublin City University</json:string><json:string>Department of Chemistry, University of Leicester, Leicester LE</json:string><json:string>Elsevier Science Ltd.</json:string><json:string>Ireland Received</json:string><json:string>Electrochem</json:string><json:string>Gooch and Housego Ltd</json:string><json:string>ILL</json:string></orgName><orgName_funder><json:string>ILL</json:string></orgName_funder><orgName_provider></orgName_provider><persName><json:string>A.R. Hillman</json:string></persName><placeName><json:string>Grenoble</json:string><json:string>UK</json:string><json:string>Dublin</json:string><json:string>Glasgow</json:string></placeName><ref_url></ref_url><ref_bibl><json:string>[4]</json:string><json:string>[23]</json:string><json:string>[29]</json:string><json:string>[22]</json:string><json:string>[28]</json:string><json:string>[1]</json:string><json:string>[24,25,27,28]</json:string><json:string>[27]</json:string><json:string>[3]</json:string><json:string>R.W. Wilson et al.</json:string><json:string>[3,4]</json:string><json:string>[5]</json:string><json:string>[14]</json:string><json:string>[2]</json:string><json:string>[24]</json:string></ref_bibl><bibl></bibl></unitex></namedEntities><ark><json:string>ark:/67375/6H6-7NHCSNMF-V</json:string></ark><categories><wos><json:string>1 - science</json:string><json:string>2 - electrochemistry</json:string></wos><scienceMetrix><json:string>1 - applied sciences</json:string><json:string>2 - enabling & strategic technologies</json:string><json:string>3 - energy</json:string></scienceMetrix><scopus><json:string>1 - Physical Sciences</json:string><json:string>2 - Chemistry</json:string><json:string>3 - Electrochemistry</json:string><json:string>1 - Physical Sciences</json:string><json:string>2 - Chemical Engineering</json:string><json:string>3 - General Chemical Engineering</json:string></scopus><inist><json:string>1 - sciences appliquees, technologies et medecines</json:string><json:string>2 - sciences biologiques et medicales</json:string><json:string>3 - sciences biologiques fondamentales et appliquees. psychologie</json:string><json:string>4 - psychologie. psychophysiologie</json:string></inist></categories><publicationDate>1999</publicationDate><copyrightDate>1999</copyrightDate><doi><json:string>10.1016/S0013-4686(99)00113-9</json:string></doi><id>B230E935257F716377AA95E118DD935BDC3CE307</id><score>1</score><fulltext><json:item><extension>pdf</extension><original>true</original><mimetype>application/pdf</mimetype><uri>https://api.istex.fr/document/B230E935257F716377AA95E118DD935BDC3CE307/fulltext/pdf</uri></json:item><json:item><extension>zip</extension><original>false</original><mimetype>application/zip</mimetype><uri>https://api.istex.fr/document/B230E935257F716377AA95E118DD935BDC3CE307/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/B230E935257F716377AA95E118DD935BDC3CE307/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a">A neutron reflectivity study of [Os(bipy)2(PVP)10Cl]+ polymer film modified electrodes: effect of redox state and counter ion</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>©1999 Elsevier Science Ltd</p></availability><date>1999</date></publicationStmt><notesStmt><note type="content">Fig. 1: Structure of the metallopolymer [Os(bipy)2(PVP)xCl]+, where bipy is the 2,2′-bipyridyl ligand, and PVP the poly(4-vinylpyridine) backbone, functionalized every x units with the osmium complex.</note><note type="content">Fig. 2: Spin coated [Os(bipy)2(PVP)10Cl]Cl film 1 in the dry state. (a) Reflectivity profile (points) and best fit (line), (b) scattering length density profile.</note><note type="content">Fig. 3: Spin coated [Os(bipy)2(PVP)10Cl]Cl film 1 in D2O. (a) Reflectivity profile (points) and best fit (line), (b) scattering length density profile.</note><note type="content">Fig. 4: Spin coated [Os(bipy)2(PVP)10Cl]Cl film 1. (a) Reflectivity profiles in D2O before redox cycling (line) and in D2O/0.1 mol dm−3 Na pTSA after redox cycling (points), (b) corresponding scattering length density profiles in D2O before redox cycling (full line) and in D2O/0.1 mol dm−3 Na pTSA after redox cycling (dashed line).</note><note type="content">Fig. 5: Reflectivity profiles for spin coated film 1 exposed to 0.1 mol dm−3 Na pTSA in: (a) D2O, (b) QCMW, (c) ACMW. In each case, the line represents data for the film maintained in the reduced state, [Os(bipy)2(PVP)10Cl]+[pTSA−], and the points represent data for the film maintained in the oxidized state, [Os(bipy)2(PVP)10Cl]2+[pTSA−]2.</note><note type="content">Fig. 6: Scattering length density profiles (derived from the data of Fig. 5) for spin coated film 1 exposed to 0.1 mol dm−3 Na pTSA in: (a) D2O, (b) QCMW, (c) ACMW. In each case, the full (dashed) line represents data for the film maintained in the reduced (oxidized) state.</note><note type="content">Fig. 7: Spin coated [Os(bipy)2(PVP)10Cl]Cl film 2 in D2O. (a) Reflectivity profile (points) and best fit (line), (b) scattering length density profile.</note><note type="content">Fig. 8: Spin coated [Os(bipy)2(PVP)10Cl]Cl film 2. (a) Reflectivity profiles in D2O before redox cycling (line) and in D2O/0.1 mol dm−3 NaClO4 after redox cycling (points), (b) corresponding scattering length density profiles in D2O before redox cycling (full line) and in D2O/0.1 mol dm−3 NaClO4 after redox cycling (dashed line).</note><note type="content">Fig. 9: Reflectivity profiles for spin coated film 2 exposed to 0.1 mol dm−3 NaClO4 in: (a) D2O, (b) QCMW, (c) ACMW. In each case, the line represents data for the film maintained in the reduced state, [Os(bipy)2(PVP)10Cl]+[ClO4−], and the points represent data for the film maintained in the oxidized state, [Os(bipy)2(PVP)10Cl]2+[ClO4−]2.</note><note type="content">Fig. 10: Scattering length density profiles (derived from the data of Fig. 9) for spin coated film 2 exposed to 0.1 mol dm−3 NaClO4 in: (a) D2O, (b) QCMW, (c) ACMW. In each case, the full (dashed) line represents data for the film maintained in the reduced (oxidized) state.</note><note type="content">Fig. 11: Cyclic voltammograms of film 1 exposed to 0.1 mol dm−3 Na pTSA/QCMW. (a) film conditioning, (b) after holding the potential at 0.0 V, (c) after holding the potential at +0.45 V. Number `1' indicates response to first half cycle.</note><note type="content">Fig. 12: Cyclic voltammograms of film 2 exposed to 0.1 mol dm−3 NaClO4/QCMW. (a) film conditioning, (b) after holding the potential at 0.0 V, (c) after holding the potential at +0.45 V. Number `1' indicates response to first half cycle.</note><note type="content">Table 1: Scattering length densities of sample constituents (calculated according to Eq. (1)</note><note type="content">Table 2: Fitted parameters to reflectivity data</note><note type="content">Table 3: Polymer volume fraction and surface coverage data</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a">A neutron reflectivity study of [Os(bipy)2(PVP)10Cl]+ polymer film modified electrodes: effect of redox state and counter ion</title><author xml:id="author-0000"><persName><forename type="first">Robert W</forename><surname>Wilson</surname></persName><affiliation>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</affiliation></author><author xml:id="author-0001"><persName><forename type="first">Robert</forename><surname>Cubitt</surname></persName><affiliation>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</affiliation></author><author xml:id="author-0002"><persName><forename type="first">Andrew</forename><surname>Glidle</surname></persName><affiliation>Bioelectronics, Glasgow University, Glasgow G12 8QQ, UK</affiliation></author><author xml:id="author-0003"><persName><forename type="first">A.Robert</forename><surname>Hillman</surname></persName><email>arh7@le.ac.uk</email><note type="correspondence"><p>Corresponding author. Tel.: +44-116-252-2144; fax: +44-116-252-3789-5227</p></note><affiliation>Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK</affiliation></author><author xml:id="author-0004"><persName><forename type="first">Paul M</forename><surname>Saville</surname></persName><affiliation>Research School of Chemistry, The Australian National University, Canberra 0200, Australia</affiliation></author><author xml:id="author-0005"><persName><forename type="first">Johannes G</forename><surname>Vos</surname></persName><affiliation>School of Chemical Sciences, Dublin City University, Dublin 9, Ireland</affiliation></author><idno type="istex">B230E935257F716377AA95E118DD935BDC3CE307</idno><idno type="DOI">10.1016/S0013-4686(99)00113-9</idno><idno type="PII">S0013-4686(99)00113-9</idno></analytic><monogr><title level="j">Electrochimica Acta</title><title level="j" type="abbrev">EA</title><idno type="pISSN">0013-4686</idno><idno type="PII">S0013-4686(00)X0080-1</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1999"></date><biblScope unit="volume">44</biblScope><biblScope unit="issue">20</biblScope><biblScope unit="page" from="3533">3533</biblScope><biblScope unit="page" to="3548">3548</biblScope></imprint></monogr></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>1999</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The effects of redox state (Os[II] vs. Os[III]) and counter ion (perchlorate vs. p-toluenesulphonate) on the polymer and solvent density distributions in films of electroactive [Os(bipy)2(PVP)10Cl]+ were determined using neutron reflectivity. The changes in polymer structure upon immersion in solvent and upon redox cycling the film in these electrolytes were also investigated. The as-prepared dry polymer film swelled appreciably upon immersion in aqueous solutions. Using p-toluenesulphonate as the counter ion caused pronounced changes to film structure upon both redox cycling and holding it in a fixed oxidation state; the perchlorate anion was found to be much less disruptive. Surprisingly, the effect on film structure of changing anion was much more pronounced than the effect of changing film redox state, i.e. charge density.</p></abstract><textClass><keywords scheme="keyword"><list><head>Keywords</head><item><term>Redox polymer</term></item><item><term>Modified electrode</term></item><item><term>Neutron reflectivity</term></item></list></keywords></textClass></profileDesc><revisionDesc><change when="1999">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><extension>txt</extension><original>false</original><mimetype>text/plain</mimetype><uri>https://api.istex.fr/document/B230E935257F716377AA95E118DD935BDC3CE307/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier, elements deleted: ce:floats; body; tail"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 4.5.2//EN//XML" URI="art452.dtd" name="istex:docType"><istex:entity SYSTEM="gr1" NDATA="IMAGE" name="gr1"></istex:entity><istex:entity SYSTEM="gr2" NDATA="IMAGE" name="gr2"></istex:entity><istex:entity SYSTEM="gr3" NDATA="IMAGE" name="gr3"></istex:entity><istex:entity SYSTEM="gr4" NDATA="IMAGE" name="gr4"></istex:entity><istex:entity SYSTEM="gr5" NDATA="IMAGE" name="gr5"></istex:entity><istex:entity SYSTEM="gr6" NDATA="IMAGE" name="gr6"></istex:entity><istex:entity SYSTEM="gr7" NDATA="IMAGE" name="gr7"></istex:entity><istex:entity SYSTEM="gr8" NDATA="IMAGE" name="gr8"></istex:entity><istex:entity SYSTEM="gr9" NDATA="IMAGE" name="gr9"></istex:entity><istex:entity SYSTEM="gr10" NDATA="IMAGE" name="gr10"></istex:entity><istex:entity SYSTEM="gr11" NDATA="IMAGE" name="gr11"></istex:entity><istex:entity SYSTEM="gr12" NDATA="IMAGE" name="gr12"></istex:entity></istex:docType><istex:document><converted-article version="4.5.2" docsubtype="fla"><item-info><jid>EA</jid><aid>2571</aid><ce:pii>S0013-4686(99)00113-9</ce:pii><ce:doi>10.1016/S0013-4686(99)00113-9</ce:doi><ce:copyright type="full-transfer" year="1999">Elsevier Science Ltd</ce:copyright></item-info><head><ce:title>A neutron reflectivity study of [Os(bipy)<ce:inf>2</ce:inf>(PVP)<ce:inf>10</ce:inf>Cl]<ce:sup>+</ce:sup> polymer film modified electrodes: effect of redox state and counter ion</ce:title><ce:author-group><ce:author><ce:given-name>Robert W</ce:given-name><ce:surname>Wilson</ce:surname><ce:cross-ref refid="AFF1"><ce:sup>a</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>Robert</ce:given-name><ce:surname>Cubitt</ce:surname><ce:cross-ref refid="AFF1"><ce:sup>a</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>Andrew</ce:given-name><ce:surname>Glidle</ce:surname><ce:cross-ref refid="AFF2"><ce:sup>b</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>A.Robert</ce:given-name><ce:surname>Hillman</ce:surname><ce:cross-ref refid="AFF3"><ce:sup>c</ce:sup></ce:cross-ref><ce:cross-ref refid="CORR1">*</ce:cross-ref><ce:e-address>arh7@le.ac.uk</ce:e-address></ce:author><ce:author><ce:given-name>Paul M</ce:given-name><ce:surname>Saville</ce:surname><ce:cross-ref refid="AFF4"><ce:sup>d</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>Johannes G</ce:given-name><ce:surname>Vos</ce:surname><ce:cross-ref refid="AFF5"><ce:sup>e</ce:sup></ce:cross-ref></ce:author><ce:affiliation id="AFF1"><ce:label>a</ce:label><ce:textfn>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</ce:textfn></ce:affiliation><ce:affiliation id="AFF2"><ce:label>b</ce:label><ce:textfn>Bioelectronics, Glasgow University, Glasgow G12 8QQ, UK</ce:textfn></ce:affiliation><ce:affiliation id="AFF3"><ce:label>c</ce:label><ce:textfn>Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK</ce:textfn></ce:affiliation><ce:affiliation id="AFF4"><ce:label>d</ce:label><ce:textfn>Research School of Chemistry, The Australian National University, Canberra 0200, Australia</ce:textfn></ce:affiliation><ce:affiliation id="AFF5"><ce:label>e</ce:label><ce:textfn>School of Chemical Sciences, Dublin City University, Dublin 9, Ireland</ce:textfn></ce:affiliation><ce:correspondence id="CORR1"><ce:label>*</ce:label><ce:text>Corresponding author. Tel.: +44-116-252-2144; fax: +44-116-252-3789-5227</ce:text></ce:correspondence></ce:author-group><ce:date-received day="27" month="11" year="1998"></ce:date-received><ce:date-accepted day="15" month="2" year="1999"></ce:date-accepted><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The effects of redox state (Os[II] vs. Os[III]) and counter ion (perchlorate vs. <ce:italic>p</ce:italic>-toluenesulphonate) on the polymer and solvent density distributions in films of electroactive [Os(bipy)<ce:inf>2</ce:inf>(PVP)<ce:inf>10</ce:inf>Cl]<ce:sup>+</ce:sup> were determined using neutron reflectivity. The changes in polymer structure upon immersion in solvent and upon redox cycling the film in these electrolytes were also investigated. The as-prepared dry polymer film swelled appreciably upon immersion in aqueous solutions. Using <ce:italic>p</ce:italic>-toluenesulphonate as the counter ion caused pronounced changes to film structure upon both redox cycling and holding it in a fixed oxidation state; the perchlorate anion was found to be much less disruptive. Surprisingly, the effect on film structure of changing anion was much more pronounced than the effect of changing film redox state, i.e. charge density.</ce:simple-para></ce:abstract-sec></ce:abstract><ce:keywords class="keyword"><ce:section-title>Keywords</ce:section-title><ce:keyword><ce:text>Redox polymer</ce:text></ce:keyword><ce:keyword><ce:text>Modified electrode</ce:text></ce:keyword><ce:keyword><ce:text>Neutron reflectivity</ce:text></ce:keyword></ce:keywords></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo><title>A neutron reflectivity study of [Os(bipy)2(PVP)10Cl]+ polymer film modified electrodes: effect of redox state and counter ion</title></titleInfo><titleInfo type="alternative" contentType="CDATA"><title>A neutron reflectivity study of [Os(bipy)</title></titleInfo><name type="personal"><namePart type="given">Robert W</namePart><namePart type="family">Wilson</namePart><affiliation>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Robert</namePart><namePart type="family">Cubitt</namePart><affiliation>Institut Laue-Langevin, B.P. 156, 38042 Grenoble, Cedex 9, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Andrew</namePart><namePart type="family">Glidle</namePart><affiliation>Bioelectronics, Glasgow University, Glasgow G12 8QQ, UK</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">A.Robert</namePart><namePart type="family">Hillman</namePart><affiliation>E-mail: arh7@le.ac.uk</affiliation><affiliation>Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK</affiliation><description>Corresponding author. Tel.: +44-116-252-2144; fax: +44-116-252-3789-5227</description><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Paul M</namePart><namePart type="family">Saville</namePart><affiliation>Research School of Chemistry, The Australian National University, Canberra 0200, Australia</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Johannes G</namePart><namePart type="family">Vos</namePart><affiliation>School of Chemical Sciences, Dublin City University, Dublin 9, Ireland</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="research-article" displayLabel="Full-length article" authority="ISTEX" authorityURI="https://content-type.data.istex.fr" valueURI="https://content-type.data.istex.fr/ark:/67375/XTP-1JC4F85T-7">research-article</genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">1999</dateIssued><copyrightDate encoding="w3cdtf">1999</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><abstract lang="en">Abstract: The effects of redox state (Os[II] vs. Os[III]) and counter ion (perchlorate vs. p-toluenesulphonate) on the polymer and solvent density distributions in films of electroactive [Os(bipy)2(PVP)10Cl]+ were determined using neutron reflectivity. The changes in polymer structure upon immersion in solvent and upon redox cycling the film in these electrolytes were also investigated. The as-prepared dry polymer film swelled appreciably upon immersion in aqueous solutions. Using p-toluenesulphonate as the counter ion caused pronounced changes to film structure upon both redox cycling and holding it in a fixed oxidation state; the perchlorate anion was found to be much less disruptive. Surprisingly, the effect on film structure of changing anion was much more pronounced than the effect of changing film redox state, i.e. charge density.</abstract><note type="content">Fig. 1: Structure of the metallopolymer [Os(bipy)2(PVP)xCl]+, where bipy is the 2,2′-bipyridyl ligand, and PVP the poly(4-vinylpyridine) backbone, functionalized every x units with the osmium complex.</note><note type="content">Fig. 2: Spin coated [Os(bipy)2(PVP)10Cl]Cl film 1 in the dry state. (a) Reflectivity profile (points) and best fit (line), (b) scattering length density profile.</note><note type="content">Fig. 3: Spin coated [Os(bipy)2(PVP)10Cl]Cl film 1 in D2O. (a) Reflectivity profile (points) and best fit (line), (b) scattering length density profile.</note><note type="content">Fig. 4: Spin coated [Os(bipy)2(PVP)10Cl]Cl film 1. (a) Reflectivity profiles in D2O before redox cycling (line) and in D2O/0.1 mol dm−3 Na pTSA after redox cycling (points), (b) corresponding scattering length density profiles in D2O before redox cycling (full line) and in D2O/0.1 mol dm−3 Na pTSA after redox cycling (dashed line).</note><note type="content">Fig. 5: Reflectivity profiles for spin coated film 1 exposed to 0.1 mol dm−3 Na pTSA in: (a) D2O, (b) QCMW, (c) ACMW. In each case, the line represents data for the film maintained in the reduced state, [Os(bipy)2(PVP)10Cl]+[pTSA−], and the points represent data for the film maintained in the oxidized state, [Os(bipy)2(PVP)10Cl]2+[pTSA−]2.</note><note type="content">Fig. 6: Scattering length density profiles (derived from the data of Fig. 5) for spin coated film 1 exposed to 0.1 mol dm−3 Na pTSA in: (a) D2O, (b) QCMW, (c) ACMW. In each case, the full (dashed) line represents data for the film maintained in the reduced (oxidized) state.</note><note type="content">Fig. 7: Spin coated [Os(bipy)2(PVP)10Cl]Cl film 2 in D2O. (a) Reflectivity profile (points) and best fit (line), (b) scattering length density profile.</note><note type="content">Fig. 8: Spin coated [Os(bipy)2(PVP)10Cl]Cl film 2. (a) Reflectivity profiles in D2O before redox cycling (line) and in D2O/0.1 mol dm−3 NaClO4 after redox cycling (points), (b) corresponding scattering length density profiles in D2O before redox cycling (full line) and in D2O/0.1 mol dm−3 NaClO4 after redox cycling (dashed line).</note><note type="content">Fig. 9: Reflectivity profiles for spin coated film 2 exposed to 0.1 mol dm−3 NaClO4 in: (a) D2O, (b) QCMW, (c) ACMW. In each case, the line represents data for the film maintained in the reduced state, [Os(bipy)2(PVP)10Cl]+[ClO4−], and the points represent data for the film maintained in the oxidized state, [Os(bipy)2(PVP)10Cl]2+[ClO4−]2.</note><note type="content">Fig. 10: Scattering length density profiles (derived from the data of Fig. 9) for spin coated film 2 exposed to 0.1 mol dm−3 NaClO4 in: (a) D2O, (b) QCMW, (c) ACMW. In each case, the full (dashed) line represents data for the film maintained in the reduced (oxidized) state.</note><note type="content">Fig. 11: Cyclic voltammograms of film 1 exposed to 0.1 mol dm−3 Na pTSA/QCMW. (a) film conditioning, (b) after holding the potential at 0.0 V, (c) after holding the potential at +0.45 V. Number `1' indicates response to first half cycle.</note><note type="content">Fig. 12: Cyclic voltammograms of film 2 exposed to 0.1 mol dm−3 NaClO4/QCMW. (a) film conditioning, (b) after holding the potential at 0.0 V, (c) after holding the potential at +0.45 V. Number `1' indicates response to first half cycle.</note><note type="content">Table 1: Scattering length densities of sample constituents (calculated according to Eq. (1)</note><note type="content">Table 2: Fitted parameters to reflectivity data</note><note type="content">Table 3: Polymer volume fraction and surface coverage data</note><subject><genre>Keywords</genre><topic>Redox polymer</topic><topic>Modified electrode</topic><topic>Neutron reflectivity</topic></subject><relatedItem type="host"><titleInfo><title>Electrochimica Acta</title></titleInfo><titleInfo type="abbreviated"><title>EA</title></titleInfo><genre type="journal" authority="ISTEX" authorityURI="https://publication-type.data.istex.fr" valueURI="https://publication-type.data.istex.fr/ark:/67375/JMC-0GLKJH51-B">journal</genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">19990601</dateIssued></originInfo><identifier type="ISSN">0013-4686</identifier><identifier type="PII">S0013-4686(00)X0080-1</identifier><part><date>19990601</date><detail type="volume"><number>44</number><caption>vol.</caption></detail><detail type="issue"><number>20</number><caption>no.</caption></detail><extent unit="issue-pages"><start>3441</start><end>3602</end></extent><extent unit="pages"><start>3533</start><end>3548</end></extent></part></relatedItem><identifier type="istex">B230E935257F716377AA95E118DD935BDC3CE307</identifier><identifier type="ark">ark:/67375/6H6-7NHCSNMF-V</identifier><identifier type="DOI">10.1016/S0013-4686(99)00113-9</identifier><identifier type="PII">S0013-4686(99)00113-9</identifier><accessCondition type="use and reproduction" contentType="copyright">©1999 Elsevier Science Ltd</accessCondition><recordInfo><recordContentSource authority="ISTEX" authorityURI="https://loaded-corpus.data.istex.fr" valueURI="https://loaded-corpus.data.istex.fr/ark:/67375/XBH-HKKZVM7B-M">elsevier</recordContentSource><recordOrigin>Elsevier Science Ltd, ©1999</recordOrigin></recordInfo></mods><json:item><extension>json</extension><original>false</original><mimetype>application/json</mimetype><uri>https://api.istex.fr/document/B230E935257F716377AA95E118DD935BDC3CE307/metadata/json</uri></json:item></metadata><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
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