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Title: 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 O 2 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/cm 2 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:
 [1];  [2];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. 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) (SC-22)
OSTI Identifier:
1501360
Grant/Contract Number:  
[SC0014176]
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
[Journal Name: ACS Catalysis]; 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:10.1021/acscatal.9b00404.
Kaminsky, Corey J., Wright, Joshua, and Surendranath, Yogesh. Mon . "Graphite-conjugation enhances porphyrin electrocatalysis". United States. doi: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 = ,
volume = ,
place = {United States},
year = {2019},
month = {3}
}

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Cited by: 6 works
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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
  • DOI: 10.1021/jacs.7b10723

    Works referencing / citing this record:

    Elucidating the origins of enhanced CO 2 reduction in manganese electrocatalysts bearing pendant hydrogen-bond donors
    journal, January 2019

    • Tignor, Steven E.; Shaw, Travis W.; Bocarsly, Andrew B.
    • Dalton Transactions, Vol. 48, Issue 33
    • DOI: 10.1039/c9dt02060h