Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation
Name
GCC-ET_Revised_Final_DSpace[1].pdf
Size
2.8 MB
Format
Adobe PDF
Checksum (MD5)
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Author(s)
Zhang, Guanghui
Miller, Jeffrey T.
Jackson, Megan
Oh, Seokjoon
Kaminsky, Corey Jarin
Chu, Sterling B
Surendranath, Yogesh
Date Issued
January 2018
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
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
Version
Author's final manuscript
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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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.
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DOI of Published Version
https://doi.org/10.1021/jacs.7b10723
