Graphite-conjugation enhances porphyrin electrocatalysis
Abstract
We synthesize porphyrins that are strongly electronically coupled to carbon electrodes by condensing diaminoporphyrin derivatives onto o-quinone moieties native to graphitic carbon surfaces. X-ray photoelectron and absorption spectroscopies along with electrochemical data establish the formation of a high-fidelity conjugated pyrazine linkage to the surface with preservation of the metalloporphyrin scaffold. Using the O2 reduction reaction (ORR) as a probe, we find that conjugation dramatically promotes the rate of catalysis. A graphite-conjugated Co porphyrin, GCC-CoTPP, displays an onset current of 10 μA/cm2 at 0.72 V versus the reversible hydrogen electrode, whereas a non-conjugated amide-linked Co-porphyrin onsets at 0.66 V. This corresponds to an order of magnitude enhancement in the activation-controlled turnover frequencies for ORR upon conjugation. Conclusively, this work establishes a versatile platform for examining the emergent reactivity of porphyrins strongly coupled to metallic electrodes.
- Authors:
-
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States); Illinois Inst. of Technology, Chicago, IL (United States)
- Publication Date:
- Research Org.:
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1501360
- Grant/Contract Number:
- SC0014176
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 30 DIRECT ENERGY CONVERSION; molecular electrocatalysis; heterogeneous electrocatalysis; oxygen reduction; porphyrin; supported catalyst; electron transfer
Citation Formats
Kaminsky, Corey J., Wright, Joshua, and Surendranath, Yogesh. Graphite-conjugation enhances porphyrin electrocatalysis. United States: N. p., 2019.
Web. doi:10.1021/acscatal.9b00404.
Kaminsky, Corey J., Wright, Joshua, & Surendranath, Yogesh. Graphite-conjugation enhances porphyrin electrocatalysis. United States. doi:https://doi.org/10.1021/acscatal.9b00404
Kaminsky, Corey J., Wright, Joshua, and Surendranath, Yogesh. Mon .
"Graphite-conjugation enhances porphyrin electrocatalysis". United States. doi:https://doi.org/10.1021/acscatal.9b00404. https://www.osti.gov/servlets/purl/1501360.
@article{osti_1501360,
title = {Graphite-conjugation enhances porphyrin electrocatalysis},
author = {Kaminsky, Corey J. and Wright, Joshua and Surendranath, Yogesh},
abstractNote = {We synthesize porphyrins that are strongly electronically coupled to carbon electrodes by condensing diaminoporphyrin derivatives onto o-quinone moieties native to graphitic carbon surfaces. X-ray photoelectron and absorption spectroscopies along with electrochemical data establish the formation of a high-fidelity conjugated pyrazine linkage to the surface with preservation of the metalloporphyrin scaffold. Using the O2 reduction reaction (ORR) as a probe, we find that conjugation dramatically promotes the rate of catalysis. A graphite-conjugated Co porphyrin, GCC-CoTPP, displays an onset current of 10 μA/cm2 at 0.72 V versus the reversible hydrogen electrode, whereas a non-conjugated amide-linked Co-porphyrin onsets at 0.66 V. This corresponds to an order of magnitude enhancement in the activation-controlled turnover frequencies for ORR upon conjugation. Conclusively, this work establishes a versatile platform for examining the emergent reactivity of porphyrins strongly coupled to metallic electrodes.},
doi = {10.1021/acscatal.9b00404},
journal = {ACS Catalysis},
number = 4,
volume = 9,
place = {United States},
year = {2019},
month = {3}
}
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Works referenced in this record:
Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation
journal, January 2018
- Jackson, Megan N.; Oh, Seokjoon; Kaminsky, Corey J.
- Journal of the American Chemical Society, Vol. 140, Issue 3
Works referencing / citing this record:
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- Angewandte Chemie, Vol. 132, Issue 12
Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide
journal, January 2020
- Smith, Peter T.; Kim, Younghoon; Benke, Bahiru Punja
- Angewandte Chemie International Edition, Vol. 59, Issue 12