Nonergodicity in nanoscale electrodes
The response of nanoscale electrodes displays deviations from conventional voltammetry theory that include a reduction in the limiting current and enhanced current fluctuations. We study the power spectra of these fluctuations in well characterized conical electrodes with radii between 2 and 10 nm....
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2013-01, Vol.15 (2), p.459-465 |
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| creator | Krapf, Diego |
| description | The response of nanoscale electrodes displays deviations from conventional voltammetry theory that include a reduction in the limiting current and enhanced current fluctuations. We study the power spectra of these fluctuations in well characterized conical electrodes with radii between 2 and 10 nm. The fluctuations are found to display non-trivial power laws. We propose a model based on reversible adsorption of the redox species onto the nanoelectrode. This model is consistent with the non-stationary character of both the limiting current and the adsorption of molecules onto metal electrodes. Our model predicts the electrochemical reaction is nonergodic and sets fundamental limits on the sensitivity of uncoated nanoelectrodes.
Faradaid currents in nanoelectrodes reveal enhanced fluctuations and exhibit aging and nonergodicity. This behaviour is explained by ionic reversible adsorption. |
| doi_str_mv | 10.1039/c2cp42838e |
| format | Article |
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Faradaid currents in nanoelectrodes reveal enhanced fluctuations and exhibit aging and nonergodicity. This behaviour is explained by ionic reversible adsorption.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/c2cp42838e</identifier><identifier>PMID: 23070026</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Adsorption ; Chemistry ; Constraining ; Deviation ; Displays ; Electrochemical Techniques - instrumentation ; Electrochemistry ; Electrodes ; Electrodes: preparations and properties ; Equipment Design ; Exact sciences and technology ; Fluctuation ; General and physical chemistry ; Mathematical models ; Models, Chemical ; Nanostructure ; Nanotechnology - instrumentation ; Oxidation-Reduction</subject><ispartof>Physical chemistry chemical physics : PCCP, 2013-01, Vol.15 (2), p.459-465</ispartof><rights>2014 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c439t-1790a685502f9492b189a5ccc51caae27e23cbffb237d7fc690146efd973a5d93</citedby><cites>FETCH-LOGICAL-c439t-1790a685502f9492b189a5ccc51caae27e23cbffb237d7fc690146efd973a5d93</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,777,781,27905,27906</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=27158495$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/23070026$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Krapf, Diego</creatorcontrib><title>Nonergodicity in nanoscale electrodes</title><title>Physical chemistry chemical physics : PCCP</title><addtitle>Phys Chem Chem Phys</addtitle><description>The response of nanoscale electrodes displays deviations from conventional voltammetry theory that include a reduction in the limiting current and enhanced current fluctuations. We study the power spectra of these fluctuations in well characterized conical electrodes with radii between 2 and 10 nm. The fluctuations are found to display non-trivial power laws. We propose a model based on reversible adsorption of the redox species onto the nanoelectrode. This model is consistent with the non-stationary character of both the limiting current and the adsorption of molecules onto metal electrodes. Our model predicts the electrochemical reaction is nonergodic and sets fundamental limits on the sensitivity of uncoated nanoelectrodes.
Faradaid currents in nanoelectrodes reveal enhanced fluctuations and exhibit aging and nonergodicity. This behaviour is explained by ionic reversible adsorption.</description><subject>Adsorption</subject><subject>Chemistry</subject><subject>Constraining</subject><subject>Deviation</subject><subject>Displays</subject><subject>Electrochemical Techniques - instrumentation</subject><subject>Electrochemistry</subject><subject>Electrodes</subject><subject>Electrodes: preparations and properties</subject><subject>Equipment Design</subject><subject>Exact sciences and technology</subject><subject>Fluctuation</subject><subject>General and physical chemistry</subject><subject>Mathematical models</subject><subject>Models, Chemical</subject><subject>Nanostructure</subject><subject>Nanotechnology - instrumentation</subject><subject>Oxidation-Reduction</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqF0TtPwzAQB3ALgWgpLOygMlRCSAE_4jgeUVQeUgUMMEfO5YyC0iTY6dBvj_ug3WCxLd1P59P_CDln9JZRoe-AQxfzVKR4QIYsTkSkaRof7t4qGZAT778opUwycUwGXFBFKU-GZPLSNug-27KCql-Oq2bcmKb1YGocY43Qu7ZEf0qOrKk9nm3vEfl4mL5nT9Hs9fE5u59FEAvdR0xpapJUSsqtjjUvWKqNBADJwBjkCrmAwtqCC1UqC4mmYUS0pVbCyFKLEbne9O1c-71A3-fzygPWtWmwXficJYrJNJY6_Z-GP2Q4JA30ZkPBtd47tHnnqrlxy5zRfJVgnvHsbZ3gNODLbd9FMcdyR38jC2CyBWYVk3Wmgcrv3XpCLYO72DjnYVfdryrUr_6q511pxQ8nVovF</recordid><startdate>20130114</startdate><enddate>20130114</enddate><creator>Krapf, Diego</creator><general>Royal Society of Chemistry</general><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7SP</scope><scope>7U5</scope><scope>8FD</scope><scope>L7M</scope></search><sort><creationdate>20130114</creationdate><title>Nonergodicity in nanoscale electrodes</title><author>Krapf, Diego</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c439t-1790a685502f9492b189a5ccc51caae27e23cbffb237d7fc690146efd973a5d93</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><topic>Adsorption</topic><topic>Chemistry</topic><topic>Constraining</topic><topic>Deviation</topic><topic>Displays</topic><topic>Electrochemical Techniques - instrumentation</topic><topic>Electrochemistry</topic><topic>Electrodes</topic><topic>Electrodes: preparations and properties</topic><topic>Equipment Design</topic><topic>Exact sciences and technology</topic><topic>Fluctuation</topic><topic>General and physical chemistry</topic><topic>Mathematical models</topic><topic>Models, Chemical</topic><topic>Nanostructure</topic><topic>Nanotechnology - instrumentation</topic><topic>Oxidation-Reduction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Krapf, Diego</creatorcontrib><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Electronics & Communications Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Krapf, Diego</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Nonergodicity in nanoscale electrodes</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><addtitle>Phys Chem Chem Phys</addtitle><date>2013-01-14</date><risdate>2013</risdate><volume>15</volume><issue>2</issue><spage>459</spage><epage>465</epage><pages>459-465</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>The response of nanoscale electrodes displays deviations from conventional voltammetry theory that include a reduction in the limiting current and enhanced current fluctuations. We study the power spectra of these fluctuations in well characterized conical electrodes with radii between 2 and 10 nm. The fluctuations are found to display non-trivial power laws. We propose a model based on reversible adsorption of the redox species onto the nanoelectrode. This model is consistent with the non-stationary character of both the limiting current and the adsorption of molecules onto metal electrodes. Our model predicts the electrochemical reaction is nonergodic and sets fundamental limits on the sensitivity of uncoated nanoelectrodes.
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| ispartof | Physical chemistry chemical physics : PCCP, 2013-01, Vol.15 (2), p.459-465 |
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| language | eng |
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| source | MEDLINE; Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Adsorption Chemistry Constraining Deviation Displays Electrochemical Techniques - instrumentation Electrochemistry Electrodes Electrodes: preparations and properties Equipment Design Exact sciences and technology Fluctuation General and physical chemistry Mathematical models Models, Chemical Nanostructure Nanotechnology - instrumentation Oxidation-Reduction |
| title | Nonergodicity in nanoscale electrodes |
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