DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 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:
 [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)
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. https://doi.org/10.1021/acscatal.9b00404
Kaminsky, Corey J., Wright, Joshua, and Surendranath, Yogesh. Mon . "Graphite-conjugation enhances porphyrin electrocatalysis". United States. 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share:

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

Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions
journal, December 2010

  • Zagal, José H.; Griveau, Sophie; Silva, J. Francisco
  • Coordination Chemistry Reviews, Vol. 254, Issue 23-24
  • DOI: 10.1016/j.ccr.2010.05.001

A review of iron and cobalt porphyrins, phthalocyanines and related complexes for electrochemical and photochemical reduction of carbon dioxide
journal, January 2015

  • Manbeck, Gerald F.; Fujita, Etsuko
  • Journal of Porphyrins and Phthalocyanines, Vol. 19, Issue 01-03
  • DOI: 10.1142/S1088424615300013

Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage
journal, September 1992


Medium Effects Are as Important as Catalyst Design for Selectivity in Electrocatalytic Oxygen Reduction by Iron–Porphyrin Complexes
journal, March 2015

  • Rigsby, Matthew L.; Wasylenko, Derek J.; Pegis, Michael L.
  • Journal of the American Chemical Society, Vol. 137, Issue 13
  • DOI: 10.1021/jacs.5b00359

Catalytic activity of cobalt and iron phthalocyanines or porphyrins supported on different carbon nanotubes towards oxygen reduction reaction
journal, November 2011


Effects of Substrate and Polymer Encapsulation on CO 2 Electroreduction by Immobilized Indium(III) Protoporphyrin
journal, April 2018


Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO 2 -to-CO Electrochemical Conversion
journal, December 2016

  • Azcarate, Iban; Costentin, Cyrille; Robert, Marc
  • Journal of the American Chemical Society, Vol. 138, Issue 51
  • DOI: 10.1021/jacs.6b07014

Oxygen reduction reactivity of cobalt(ii) hangman porphyrins
journal, January 2010

  • McGuire Jr., Robert; Dogutan, Dilek K.; Teets, Thomas S.
  • Chemical Science, Vol. 1, Issue 3
  • DOI: 10.1039/c0sc00281j

Molecular Catalysts for Multielectron Redox Reactions of Small Molecules: The“Cofacial Metallodiporphyrin” Approach
journal, September 1994

  • Collman, James P.; Wagenknecht, Paul S.; Hutchison, James E.
  • Angewandte Chemie International Edition in English, Vol. 33, Issue 1516
  • DOI: 10.1002/anie.199415371

Homogenous Electrocatalytic Oxygen Reduction Rates Correlate with Reaction Overpotential in Acidic Organic Solutions
journal, October 2016


Graphite-Conjugated Pyrazines as Molecularly Tunable Heterogeneous Electrocatalysts
journal, August 2015

  • Fukushima, Tomohiro; Drisdell, Walter; Yano, Junko
  • Journal of the American Chemical Society, Vol. 137, Issue 34
  • DOI: 10.1021/jacs.5b06737

Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction
journal, February 2016

  • Oh, Seokjoon; Gallagher, James R.; Miller, Jeffrey T.
  • Journal of the American Chemical Society, Vol. 138, Issue 6
  • DOI: 10.1021/jacs.5b13080

Molecular-Level Insights into Oxygen Reduction Catalysis by Graphite-Conjugated Active Sites
journal, October 2017

  • Ricke, Nathan D.; Murray, Alexander T.; Shepherd, James J.
  • ACS Catalysis, Vol. 7, Issue 11
  • DOI: 10.1021/acscatal.7b03086

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

Synthesis of porphyrin-2,3,12,13- and -2,3,7,8-tetraones: building blocks for the synthesis of extended porphyrin arrays
journal, January 1995

  • Crossley, Maxwell J.; Govenlock, Linda J.; Prashar, Jognandan K.
  • Journal of the Chemical Society, Chemical Communications, Issue 23
  • DOI: 10.1039/c39950002379

The synthesis and studies towards the self-replication of bis(capped porphyrins)
journal, March 2003

  • Thordarson, Pall; Marquis, Annie; Crossley, Maxwell J.
  • Organic & Biomolecular Chemistry, Vol. 1, Issue 7
  • DOI: 10.1039/b211015f

Biomimetic Studies of Terminal Oxidases:  Trisimidazole Picket Metalloporphyrins
journal, March 2002

  • Collman, James P.; Sunderland, Christopher J.; Boulatov, Roman
  • Inorganic Chemistry, Vol. 41, Issue 8
  • DOI: 10.1021/ic011191p

The Crystal and Molecular Structure of Chloro-α,β,γ,δ-tetraphenylporphinatocobalt(III)
journal, November 1976

  • Sakurai, Tosio; Yamamoto, Kiyoko; Naito, Hirobumi
  • Bulletin of the Chemical Society of Japan, Vol. 49, Issue 11
  • DOI: 10.1246/bcsj.49.3042

New strategies for electrocatalysis at polymer-coated electrodes. Reduction of dioxygen by cobalt porphyrins immobilized in Nafion coatings on graphite electrodes
journal, January 1984

  • Buttry, Daniel A.; Anson, Fred C.
  • Journal of the American Chemical Society, Vol. 106, Issue 1
  • DOI: 10.1021/ja00313a013

Comparison of the Behavior of Several Cobalt Porphyrins as Electrocatalysts for the Reduction of O 2 at Graphite Electrodes
journal, July 1998

  • Song, Euihwan; Shi, Chunnian; Anson, Fred C.
  • Langmuir, Vol. 14, Issue 15
  • DOI: 10.1021/la980084d

Diverse porphyrin dimers as candidates for high-density charge-storage molecules
journal, January 2006

  • Lysenko, Andrey B.; Thamyongkit, Patchanita; Schmidt, Izabela
  • Journal of Porphyrins and Phthalocyanines, Vol. 10, Issue 01
  • DOI: 10.1142/S1088424606000041

Chemically modified carbon electrodes
journal, June 1979

  • Rocklin, Roy D.; Murray, Royce W.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 100, Issue 1-2
  • DOI: 10.1016/S0022-0728(79)80168-0

Electron Transfer and Axial Coordination Reactions of Cobalt Tetra(Aminophenyl)Porphyrins Covalently Bonded to Carbon Electrodes
journal, September 1980

  • Jester, Colleen P.; Rocklin, Roy D.; Murray, Royce W.
  • Journal of The Electrochemical Society, Vol. 127, Issue 9
  • DOI: 10.1149/1.2130048

Role of Proton-Coupled Electron Transfer in O–O Bond Activation
journal, July 2007

  • Rosenthal, Joel; Nocera, Daniel G.
  • Accounts of Chemical Research, Vol. 40, Issue 7
  • DOI: 10.1021/ar7000638

Works referencing / citing this record:

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
  • DOI: 10.1002/anie.201916131

Liquefied Sunshine: Transforming Renewables into Fertilizers and Energy Carriers with Electromaterials
journal, November 2019

  • MacFarlane, Douglas R.; Choi, Jaecheol; Suryanto, Bryan H. R.
  • Advanced Materials, Vol. 32, Issue 18
  • DOI: 10.1002/adma.201904804

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, Vol. 132, Issue 12
  • DOI: 10.1002/ange.201916131

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