Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation
Abstract
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.
- Authors:
-
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
- Purdue Univ., West Lafayette, IN (United States). Chemical Engineering
- Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1438889
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 3; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Jackson, Megan N., Oh, Seokjoon, Kaminsky, Corey J., Chu, Sterling B., Zhang, Guanghui, Miller, Jeffrey T., and Surendranath, Yogesh. Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation. United States: N. p., 2018.
Web. doi:10.1021/jacs.7b10723.
Jackson, Megan N., Oh, Seokjoon, Kaminsky, Corey J., Chu, Sterling B., Zhang, Guanghui, Miller, Jeffrey T., & Surendranath, Yogesh. Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation. United States. https://doi.org/10.1021/jacs.7b10723
Jackson, Megan N., Oh, Seokjoon, Kaminsky, Corey J., Chu, Sterling B., Zhang, Guanghui, Miller, Jeffrey T., and Surendranath, Yogesh. Mon .
"Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation". United States. https://doi.org/10.1021/jacs.7b10723. https://www.osti.gov/servlets/purl/1438889.
@article{osti_1438889,
title = {Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation},
author = {Jackson, Megan N. and Oh, Seokjoon and Kaminsky, Corey J. and Chu, Sterling B. and Zhang, Guanghui and Miller, Jeffrey T. and Surendranath, Yogesh},
abstractNote = {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.},
doi = {10.1021/jacs.7b10723},
journal = {Journal of the American Chemical Society},
number = 3,
volume = 140,
place = {United States},
year = {Mon Jan 08 00:00:00 EST 2018},
month = {Mon Jan 08 00:00:00 EST 2018}
}
Web of Science
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