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barrier for electron transfer and O2 activation.21 Together, these
data highlight that GCPs can display potent multielectron
reactivity, which is absent in discrete molecular analogs.
In conclusion, we have demonstrated that simple ortho-
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quinone functionalities found ubiquitously on edge planes of
graphitic carbons. As prepared, the resulting GCP units exhibit
high activity for oxygen reduction catalysis. Owing to the
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oxygen reduction catalysis can be systemically decreased by
increasing the electrophilicity of the pyrazine core, reaching per
site turnover frequencies rivaling metallic polycrystalline silver.
Interestingly, GCPs display higher catalytic activity than discrete
homogeneous molecular analogs bearing identical functionality.
Given their facile preparation and the wide array of accessible
phenylenediamine derivatives, GCPs are poised to serve as a
powerful platform for constructing molecularly well-defined,
tunable heterogeneous catalysts.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
Experimental details, synthesis and characterization data
for molecular precursors, XPS, XANES, elemental analysis
of high surface area carbons, and additional electro-
chemical characterization data (PDF)
(11) Thorogood, C. A.; Wildgoose, G. G.; Crossley, A.; Jacobs, R. M. J.;
Jones, J. H.; Compton, R. G. Chem. Mater. 2007, 19, 4964−4974.
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AUTHOR INFORMATION
Corresponding Author
■
(13) (a) Arrigo, R.; Havecker, M.; Wrabetz, S.; Blume, R.; Lerch, M.;
̈
McGregor, J.; Parrott, E. P. J.; Zeitler, J. A.; Gladden, L. F.; Knop-
Gericke, R.; Schlogl, R.; Su, D. S. J. Am. Chem. Soc. 2010, 132, 9616−
̈
Notes
9630. (b) Li, Q.; Noffke, B. W.; Wang, Y.; Menezes; Peters, D. G.;
Raghavachari, K.; Li, L.-S. J. Am. Chem. Soc. 2014, 136, 3358−3361.
(14) Mitra-Kirtley, S.; Mullins, O. C.; Van Elp, J.; George, S. J.; Chen,
J.; Cramer, S. P. J. Am. Chem. Soc. 1993, 115, 252−258.
(15) Fitton, A. O.; Smalley, R. K. Practical Heterocyclic Chemistry;
Academic Press, Inc.: London, 1968.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
T.F. thanks Y. Inamoto, K. Kawasumi, and M. Risch for fruitful
discussions. This work was supported by a JSPS postdoctoral
fellowship for research abroad for T.F. This work was also
supported by the U.S. Department of Energy, Office of Science,
Office of Basic Energy Sciences, under award number DE-
SC0014176 and by the MIT Department of Chemistry through
junior faculty funds for Y.S. XAS experiments were supported by
the Joint Center for Artificial Photosynthesis, a DOE Energy
Innovation Hub, supported through the Office of Science of the
U.S. Department of Energy under award no. DE-SC0004993 and
performed at the Advanced Light Source (BL 6.3.1), Berkeley,
under contract DE-AC02-05CH11231.
(16) Bard, A. J.; Faulkner, L. R. Electrochemical Methods: Fundamentals
and Applications, 2nd ed.; Wiley-VCH: New York, 2001; p 591.
(17) Chidsey, C. E. D.; Bertozzi, C. R.; Putvinski, T. M.; Mujsce, A. M.
J. Am. Chem. Soc. 1990, 112, 4301−4306.
(18) Wuttig, A.; Surendranath, Y. ACS Catal. 2015, 5, 4479−4484.
(19) Gileadi, E. Physical Electrochemistry: Fundamentals, Techniques and
Applications; Wiley-VCH: New York.
(20) Vanderwal, C. D. J. Org. Chem. 2011, 76, 9555−9567.
(21) Li, Q.; Zhang, S.; Dai, L.; Li, L.-S. J. Am. Chem. Soc. 2012, 134,
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