Spectroelectrochemical detection of specifically adsorbed cyanurate anions at gold electrodes with (111) orientation in contact with cyanate and cyanuric acid neutral solutions
The adsorption and reactivity of cyanate at Au(111) single crystal and Au(111)-25nm thin film electrodes is studied spectroelectrochemically in sodium perchlorate solutions and compared to those of cyanuric acid (C3N3O3H3). From the Surface Enhanced Infrared Reflection Absorption spectra obtained un...
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| Veröffentlicht in: | Journal of electroanalytical chemistry (Lausanne, Switzerland) Switzerland), 2017-09, Vol.800, p.167-175 |
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| creator | Cheuquepán, William Rodes, Antonio Orts, José M. Feliu, Juan M. |
| description | The adsorption and reactivity of cyanate at Au(111) single crystal and Au(111)-25nm thin film electrodes is studied spectroelectrochemically in sodium perchlorate solutions and compared to those of cyanuric acid (C3N3O3H3). From the Surface Enhanced Infrared Reflection Absorption spectra obtained under Attenuated Total Reflection conditions (ATR-SEIRAS) it can be concluded that adsorbed cyanate species predominate at the electrode surface for low cyanate concentrations. However, for cyanate concentrations above 1mM, the similarity of the ATR-SEIRA spectra with those obtained in cyanuric acid containing solutions indicates that some species coming from cyanuric acid is formed and adsorbed at the (111) gold surface sites as the result of an electroless trimerization reaction. Taking into account the results of Density Functional Theory (DFT) calculations, the experimental voltammetric and ATR-SEIRAS results agree with the formation of adlayers of specifically adsorbed triketo-monocyanurate species that adsorb perpendicular to the electrode surface.
•N-bonded cyanate forms at Au(111) in the presence of low cyanate concentrations.•Specifically adsorbed triketo-monocyanurate is formed for higher concentrations.•Undissociated triketo cyanuric acid interacts weakly with the Au(111) surface. |
| doi_str_mv | 10.1016/j.jelechem.2017.02.015 |
| format | Article |
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•N-bonded cyanate forms at Au(111) in the presence of low cyanate concentrations.•Specifically adsorbed triketo-monocyanurate is formed for higher concentrations.•Undissociated triketo cyanuric acid interacts weakly with the Au(111) surface.</description><identifier>ISSN: 1572-6657</identifier><identifier>EISSN: 1873-2569</identifier><identifier>DOI: 10.1016/j.jelechem.2017.02.015</identifier><language>eng</language><publisher>Amsterdam: Elsevier B.V</publisher><subject>Absorption spectra ; Adsorption ; ATR-SEIRAS ; Cyanate ; Cyanates ; Cyanuric acid ; Density functional theory ; DFT ; Electrodes ; Gold ; Infrared reflection ; Infrared spectra ; Oxidation ; Single crystals ; Sodium perchlorate ; Thin films</subject><ispartof>Journal of electroanalytical chemistry (Lausanne, Switzerland), 2017-09, Vol.800, p.167-175</ispartof><rights>2017 Elsevier B.V.</rights><rights>Copyright Elsevier Science Ltd. Sep 1, 2017</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c340t-9bfdefdbbc9ca23686b4a4190a30637d924164d4a88166a3ba37fa6774c44cb73</citedby><cites>FETCH-LOGICAL-c340t-9bfdefdbbc9ca23686b4a4190a30637d924164d4a88166a3ba37fa6774c44cb73</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.jelechem.2017.02.015$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,780,784,3548,27923,27924,45994</link.rule.ids></links><search><creatorcontrib>Cheuquepán, William</creatorcontrib><creatorcontrib>Rodes, Antonio</creatorcontrib><creatorcontrib>Orts, José M.</creatorcontrib><creatorcontrib>Feliu, Juan M.</creatorcontrib><title>Spectroelectrochemical detection of specifically adsorbed cyanurate anions at gold electrodes with (111) orientation in contact with cyanate and cyanuric acid neutral solutions</title><title>Journal of electroanalytical chemistry (Lausanne, Switzerland)</title><description>The adsorption and reactivity of cyanate at Au(111) single crystal and Au(111)-25nm thin film electrodes is studied spectroelectrochemically in sodium perchlorate solutions and compared to those of cyanuric acid (C3N3O3H3). From the Surface Enhanced Infrared Reflection Absorption spectra obtained under Attenuated Total Reflection conditions (ATR-SEIRAS) it can be concluded that adsorbed cyanate species predominate at the electrode surface for low cyanate concentrations. However, for cyanate concentrations above 1mM, the similarity of the ATR-SEIRA spectra with those obtained in cyanuric acid containing solutions indicates that some species coming from cyanuric acid is formed and adsorbed at the (111) gold surface sites as the result of an electroless trimerization reaction. Taking into account the results of Density Functional Theory (DFT) calculations, the experimental voltammetric and ATR-SEIRAS results agree with the formation of adlayers of specifically adsorbed triketo-monocyanurate species that adsorb perpendicular to the electrode surface.
•N-bonded cyanate forms at Au(111) in the presence of low cyanate concentrations.•Specifically adsorbed triketo-monocyanurate is formed for higher concentrations.•Undissociated triketo cyanuric acid interacts weakly with the Au(111) surface.</description><subject>Absorption spectra</subject><subject>Adsorption</subject><subject>ATR-SEIRAS</subject><subject>Cyanate</subject><subject>Cyanates</subject><subject>Cyanuric acid</subject><subject>Density functional theory</subject><subject>DFT</subject><subject>Electrodes</subject><subject>Gold</subject><subject>Infrared reflection</subject><subject>Infrared spectra</subject><subject>Oxidation</subject><subject>Single crystals</subject><subject>Sodium perchlorate</subject><subject>Thin films</subject><issn>1572-6657</issn><issn>1873-2569</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNqFkcFu1TAQRSNEJUrhF5AlNrBIsB0_-2UHqtqCVKkLYG1N7Al1lMYP26F6f9VP7KRp16xsj-49tu-tqg-CN4IL_WVsRpzQ3eJdI7kwDZcNF7tX1anYm7aWO929pv3OyFrrnXlTvc155Fzu90KeVg8_D-hKiiuBlpUSHEzMY6FBiDOLA8ukCcM6n44MfI6pR8_cEeYlQUEGMwkzg8L-xMmzZ5bHzO5DuWWfhBCfWUwB5wJPzDAzF-ngyqZYURvoBRscAxc8m3Epid6T47Ss1vyuOhlgyvj-eT2rfl9e_Dr_Xl_fXP04_3Zdu1bxUnf94HHwfe86B7LVe90rUKLj0HLdGt9JJbTyCigGraHtoTUDaGOUU8r1pj2rPm7cQ4p_F8zFjnFJM11pJTfkonQ7UulN5VLMOeFgDyncQTpawe3ajh3tSzt2bcdyaakdMn7djEh_-Bcw2ewoH4c-JErP-hj-h3gEpsGgtQ</recordid><startdate>20170901</startdate><enddate>20170901</enddate><creator>Cheuquepán, William</creator><creator>Rodes, Antonio</creator><creator>Orts, José M.</creator><creator>Feliu, Juan M.</creator><general>Elsevier B.V</general><general>Elsevier Science Ltd</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20170901</creationdate><title>Spectroelectrochemical detection of specifically adsorbed cyanurate anions at gold electrodes with (111) orientation in contact with cyanate and cyanuric acid neutral solutions</title><author>Cheuquepán, William ; Rodes, Antonio ; Orts, José M. ; Feliu, Juan M.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c340t-9bfdefdbbc9ca23686b4a4190a30637d924164d4a88166a3ba37fa6774c44cb73</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Absorption spectra</topic><topic>Adsorption</topic><topic>ATR-SEIRAS</topic><topic>Cyanate</topic><topic>Cyanates</topic><topic>Cyanuric acid</topic><topic>Density functional theory</topic><topic>DFT</topic><topic>Electrodes</topic><topic>Gold</topic><topic>Infrared reflection</topic><topic>Infrared spectra</topic><topic>Oxidation</topic><topic>Single crystals</topic><topic>Sodium perchlorate</topic><topic>Thin films</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Cheuquepán, William</creatorcontrib><creatorcontrib>Rodes, Antonio</creatorcontrib><creatorcontrib>Orts, José M.</creatorcontrib><creatorcontrib>Feliu, Juan M.</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Journal of electroanalytical chemistry (Lausanne, Switzerland)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Cheuquepán, William</au><au>Rodes, Antonio</au><au>Orts, José M.</au><au>Feliu, Juan M.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Spectroelectrochemical detection of specifically adsorbed cyanurate anions at gold electrodes with (111) orientation in contact with cyanate and cyanuric acid neutral solutions</atitle><jtitle>Journal of electroanalytical chemistry (Lausanne, Switzerland)</jtitle><date>2017-09-01</date><risdate>2017</risdate><volume>800</volume><spage>167</spage><epage>175</epage><pages>167-175</pages><issn>1572-6657</issn><eissn>1873-2569</eissn><abstract>The adsorption and reactivity of cyanate at Au(111) single crystal and Au(111)-25nm thin film electrodes is studied spectroelectrochemically in sodium perchlorate solutions and compared to those of cyanuric acid (C3N3O3H3). From the Surface Enhanced Infrared Reflection Absorption spectra obtained under Attenuated Total Reflection conditions (ATR-SEIRAS) it can be concluded that adsorbed cyanate species predominate at the electrode surface for low cyanate concentrations. However, for cyanate concentrations above 1mM, the similarity of the ATR-SEIRA spectra with those obtained in cyanuric acid containing solutions indicates that some species coming from cyanuric acid is formed and adsorbed at the (111) gold surface sites as the result of an electroless trimerization reaction. Taking into account the results of Density Functional Theory (DFT) calculations, the experimental voltammetric and ATR-SEIRAS results agree with the formation of adlayers of specifically adsorbed triketo-monocyanurate species that adsorb perpendicular to the electrode surface.
•N-bonded cyanate forms at Au(111) in the presence of low cyanate concentrations.•Specifically adsorbed triketo-monocyanurate is formed for higher concentrations.•Undissociated triketo cyanuric acid interacts weakly with the Au(111) surface.</abstract><cop>Amsterdam</cop><pub>Elsevier B.V</pub><doi>10.1016/j.jelechem.2017.02.015</doi><tpages>9</tpages></addata></record> |
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| subjects | Absorption spectra Adsorption ATR-SEIRAS Cyanate Cyanates Cyanuric acid Density functional theory DFT Electrodes Gold Infrared reflection Infrared spectra Oxidation Single crystals Sodium perchlorate Thin films |
| title | Spectroelectrochemical detection of specifically adsorbed cyanurate anions at gold electrodes with (111) orientation in contact with cyanate and cyanuric acid neutral solutions |
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