Graphite-Conjugated Pyrazines as Molecularly Tunable Heterogeneous Electrocatalysts
Abstract
Condensation of ortho-phenylenediamine derivatives with ortho-quinone moieties at edge planes of graphitic carbon generates graphite-conjugated pyrazines (GCPs) that are active for oxygen reduction electrocatalysis in alkaline aqueous electrolyte. Catalytic rates of oxygen reduction are positively correlated with the electrophilicity of the active site pyrazine unit and can be tuned by over 70-fold by appending electron-withdrawing substituents to the phenylenediamine precursors. Discrete molecular analogs containing pyrazine moieties display no activity above background under identical conditions. This simple bottom up method for constructing molecularly well-defined active sites on ubiquitous graphitic solids enables here the rational design of tunable heterogeneous catalysts.
- Authors:
-
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis. Physical Biosciences Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1512247
- Grant/Contract Number:
- AC02-05CH11231; SC0014176; SC0004993
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 137; Journal Issue: 34; 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
Fukushima, Tomohiro, Drisdell, Walter, Yano, Junko, and Surendranath, Yogesh. Graphite-Conjugated Pyrazines as Molecularly Tunable Heterogeneous Electrocatalysts. United States: N. p., 2015.
Web. doi:10.1021/jacs.5b06737.
Fukushima, Tomohiro, Drisdell, Walter, Yano, Junko, & Surendranath, Yogesh. Graphite-Conjugated Pyrazines as Molecularly Tunable Heterogeneous Electrocatalysts. United States. https://doi.org/10.1021/jacs.5b06737
Fukushima, Tomohiro, Drisdell, Walter, Yano, Junko, and Surendranath, Yogesh. Fri .
"Graphite-Conjugated Pyrazines as Molecularly Tunable Heterogeneous Electrocatalysts". United States. https://doi.org/10.1021/jacs.5b06737. https://www.osti.gov/servlets/purl/1512247.
@article{osti_1512247,
title = {Graphite-Conjugated Pyrazines as Molecularly Tunable Heterogeneous Electrocatalysts},
author = {Fukushima, Tomohiro and Drisdell, Walter and Yano, Junko and Surendranath, Yogesh},
abstractNote = {Condensation of ortho-phenylenediamine derivatives with ortho-quinone moieties at edge planes of graphitic carbon generates graphite-conjugated pyrazines (GCPs) that are active for oxygen reduction electrocatalysis in alkaline aqueous electrolyte. Catalytic rates of oxygen reduction are positively correlated with the electrophilicity of the active site pyrazine unit and can be tuned by over 70-fold by appending electron-withdrawing substituents to the phenylenediamine precursors. Discrete molecular analogs containing pyrazine moieties display no activity above background under identical conditions. This simple bottom up method for constructing molecularly well-defined active sites on ubiquitous graphitic solids enables here the rational design of tunable heterogeneous catalysts.},
doi = {10.1021/jacs.5b06737},
journal = {Journal of the American Chemical Society},
number = 34,
volume = 137,
place = {United States},
year = {Fri Aug 21 00:00:00 EDT 2015},
month = {Fri Aug 21 00:00:00 EDT 2015}
}
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Figures / Tables:
Scheme 1: Condensation of ortho-‐phenylenediamine derivatives with ortho-‐quinone edge sites of graphene sheets to generate graphite-‐conjugated pyrazines (GCPs).
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