Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation
Glassy carbon electrodes were functionalized with redox-active moieties by condensation of o-phenylenediamine derivatives with o-quinone sites native to graphitic carbon surfaces. Electrochemical and spectroscopic investigations establish that these graphite-conjugated catalysts (GCCs) exhibit stron...
| Main Authors: | , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2018
|
| Online Access: | http://hdl.handle.net/1721.1/119426 https://orcid.org/0000-0002-7978-5212 https://orcid.org/0000-0002-8980-5213 https://orcid.org/0000-0003-4783-4734 https://orcid.org/0000-0003-1016-3420 |
| _version_ | 1811096341810511872 |
|---|---|
| author | Zhang, Guanghui Miller, Jeffrey T. Jackson, Megan Oh, Seokjoon Kaminsky, Corey Jarin Chu, Sterling B Surendranath, Yogesh |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Zhang, Guanghui Miller, Jeffrey T. Jackson, Megan Oh, Seokjoon Kaminsky, Corey Jarin Chu, Sterling B Surendranath, Yogesh |
| author_sort | Zhang, Guanghui |
| collection | MIT |
| description | Glassy carbon electrodes were functionalized with redox-active moieties by condensation of o-phenylenediamine derivatives with o-quinone sites native to graphitic carbon surfaces. Electrochemical and spectroscopic investigations establish that these graphite-conjugated catalysts (GCCs) exhibit strong electronic coupling to the electrode, leading to electron transfer (ET) behavior that diverges fundamentally from that of solution-phase or surface-tethered analogues. We find that (1) ET is not observed between the electrode and a redox-active GCC moiety regardless of applied potential. (2) ET is observed at GCCs only if the interfacial reaction is ion-coupled. (3) Even when ET is observed, the oxidation state of a transition metal GCC site remains unchanged. From these observations, we construct a mechanistic model for GCC sites in which ET behavior is identical to that of catalytically active metal surfaces rather than to that of molecules in solution. These results suggest that GCCs provide a versatile platform for bridging molecular and heterogeneous electrocatalysis. |
| first_indexed | 2024-09-23T16:42:18Z |
| format | Article |
| id | mit-1721.1/119426 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T16:42:18Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1194262022-09-29T20:55:34Z Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation Zhang, Guanghui Miller, Jeffrey T. Jackson, Megan Oh, Seokjoon Kaminsky, Corey Jarin Chu, Sterling B Surendranath, Yogesh Massachusetts Institute of Technology. Department of Chemistry Surendranath, Yogesh Jackson, Megan Oh, Seokjoon Kaminsky, Corey Jarin Chu, Sterling B Surendranath, Yogesh Glassy carbon electrodes were functionalized with redox-active moieties by condensation of o-phenylenediamine derivatives with o-quinone sites native to graphitic carbon surfaces. Electrochemical and spectroscopic investigations establish that these graphite-conjugated catalysts (GCCs) exhibit strong electronic coupling to the electrode, leading to electron transfer (ET) behavior that diverges fundamentally from that of solution-phase or surface-tethered analogues. We find that (1) ET is not observed between the electrode and a redox-active GCC moiety regardless of applied potential. (2) ET is observed at GCCs only if the interfacial reaction is ion-coupled. (3) Even when ET is observed, the oxidation state of a transition metal GCC site remains unchanged. From these observations, we construct a mechanistic model for GCC sites in which ET behavior is identical to that of catalytically active metal surfaces rather than to that of molecules in solution. These results suggest that GCCs provide a versatile platform for bridging molecular and heterogeneous electrocatalysis. United States. Department of Energy. Office of Basic Energy Sciences (Award DE-SC0014176) National Science Foundation (U.S.) (Grant 1122374) 2018-12-04T18:40:17Z 2018-12-04T18:40:17Z 2018-01 2017-10 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/119426 Jackson, Megan N. et al. “Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation.” Journal of the American Chemical Society 140, 3 (January 2018): 1004–1010 © 2017 American Chemical Society https://orcid.org/0000-0002-7978-5212 https://orcid.org/0000-0002-8980-5213 https://orcid.org/0000-0003-4783-4734 https://orcid.org/0000-0003-1016-3420 en_US http://dx.doi.org/10.1021/jacs.7b10723 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) Prof. Surendranath via Erja Kajosalo |
| spellingShingle | Zhang, Guanghui Miller, Jeffrey T. Jackson, Megan Oh, Seokjoon Kaminsky, Corey Jarin Chu, Sterling B Surendranath, Yogesh Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation |
| title | Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation |
| title_full | Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation |
| title_fullStr | Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation |
| title_full_unstemmed | Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation |
| title_short | Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation |
| title_sort | strong electronic coupling of molecular sites to graphitic electrodes via pyrazine conjugation |
| url | http://hdl.handle.net/1721.1/119426 https://orcid.org/0000-0002-7978-5212 https://orcid.org/0000-0002-8980-5213 https://orcid.org/0000-0003-4783-4734 https://orcid.org/0000-0003-1016-3420 |
| work_keys_str_mv | AT zhangguanghui strongelectroniccouplingofmolecularsitestographiticelectrodesviapyrazineconjugation AT millerjeffreyt strongelectroniccouplingofmolecularsitestographiticelectrodesviapyrazineconjugation AT jacksonmegan strongelectroniccouplingofmolecularsitestographiticelectrodesviapyrazineconjugation AT ohseokjoon strongelectroniccouplingofmolecularsitestographiticelectrodesviapyrazineconjugation AT kaminskycoreyjarin strongelectroniccouplingofmolecularsitestographiticelectrodesviapyrazineconjugation AT chusterlingb strongelectroniccouplingofmolecularsitestographiticelectrodesviapyrazineconjugation AT surendranathyogesh strongelectroniccouplingofmolecularsitestographiticelectrodesviapyrazineconjugation |