Graphite-conjugation enhances porphyrin electrocatalysis

Kaminsky, Corey J.; Wright, Joshua; Surendranath, Yogesh

doi:10.1021/acscatal.9b00404

Title: Graphite-conjugation enhances porphyrin electrocatalysis

Journal Article · Mon Mar 11 00:00:00 EDT 2019 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b00404· OSTI ID:1501360

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)

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.

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0014176

OSTI ID:: 1501360

Journal Information:: ACS Catalysis, Vol. 9, Issue 4; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 47 works

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Elucidating the origins of enhanced CO ₂ reduction in manganese electrocatalysts bearing pendant hydrogen-bond donors Tignor, Steven E.; Shaw, Travis W.; Bocarsly, Andrew B. Dalton Transactions, Vol. 48, Issue 33 https://doi.org/10.1039/c9dt02060h	journal	January 2019

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