Graphite-conjugation enhances porphyrin electrocatalysis

doi:10.1021/acscatal.9b00404

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:

Kaminsky, Corey J. ^[1]; Wright, Joshua ^[2]; Surendranath, Yogesh ^[1]

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:: 2019-03-11

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.

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                    Kaminsky, Corey J., Wright, Joshua, & Surendranath, Yogesh. Graphite-conjugation enhances porphyrin electrocatalysis.  United States.  doi:10.1021/acscatal.9b00404.

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                    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.

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@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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DOI: 10.1021/acscatal.9b00404

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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

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Abstract

Citation Formats

Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation journal, January 2018

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

Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation
journal, January 2018

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