Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation
Abstract
Glassy carbon electrodes were functionalized with redox-active moieties by condensation of o-phenylenediamine derivatives with o-quinone sites native to graphitic carbon surfaces. Electrochemical and spectroscopic investigations establish that these graphite-conjugated catalysts (GCCs) exhibit strong electronic coupling to the electrode, leading to electron transfer (ET) behavior that diverges fundamentally from that of solution-phase or surface-tethered analogues. We find that (1) ET is not observed between the electrode and a redox-active GCC moiety regardless of applied potential. (2) ET is observed at GCCs only if the interfacial reaction is ion-coupled. (3) Even when ET is observed, the oxidation state of a transition metal GCC site remains unchanged. From these observations, we construct a mechanistic model for GCC sites in which ET behavior is identical to that of catalytically active metal surfaces rather than to that of molecules in solution. These results suggest that GCCs provide a versatile platform for bridging molecular and heterogeneous electrocatalysis.
- Authors:
-
[1];
[2];
[1]
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
- Purdue Univ., West Lafayette, IN (United States). Chemical Engineering
- Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1438889
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 3; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Jackson, Megan N., Oh, Seokjoon, Kaminsky, Corey J., Chu, Sterling B., Zhang, Guanghui, Miller, Jeffrey T., and Surendranath, Yogesh. Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation. United States: N. p., 2018.
Web. doi:10.1021/jacs.7b10723.
Jackson, Megan N., Oh, Seokjoon, Kaminsky, Corey J., Chu, Sterling B., Zhang, Guanghui, Miller, Jeffrey T., & Surendranath, Yogesh. Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation. United States. https://doi.org/10.1021/jacs.7b10723
Jackson, Megan N., Oh, Seokjoon, Kaminsky, Corey J., Chu, Sterling B., Zhang, Guanghui, Miller, Jeffrey T., and Surendranath, Yogesh. Mon .
"Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation". United States. https://doi.org/10.1021/jacs.7b10723. https://www.osti.gov/servlets/purl/1438889.
@article{osti_1438889,
title = {Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation},
author = {Jackson, Megan N. and Oh, Seokjoon and Kaminsky, Corey J. and Chu, Sterling B. and Zhang, Guanghui and Miller, Jeffrey T. and Surendranath, Yogesh},
abstractNote = {Glassy carbon electrodes were functionalized with redox-active moieties by condensation of o-phenylenediamine derivatives with o-quinone sites native to graphitic carbon surfaces. Electrochemical and spectroscopic investigations establish that these graphite-conjugated catalysts (GCCs) exhibit strong electronic coupling to the electrode, leading to electron transfer (ET) behavior that diverges fundamentally from that of solution-phase or surface-tethered analogues. We find that (1) ET is not observed between the electrode and a redox-active GCC moiety regardless of applied potential. (2) ET is observed at GCCs only if the interfacial reaction is ion-coupled. (3) Even when ET is observed, the oxidation state of a transition metal GCC site remains unchanged. From these observations, we construct a mechanistic model for GCC sites in which ET behavior is identical to that of catalytically active metal surfaces rather than to that of molecules in solution. These results suggest that GCCs provide a versatile platform for bridging molecular and heterogeneous electrocatalysis.},
doi = {10.1021/jacs.7b10723},
journal = {Journal of the American Chemical Society},
number = 3,
volume = 140,
place = {United States},
year = {Mon Jan 08 00:00:00 EST 2018},
month = {Mon Jan 08 00:00:00 EST 2018}
}
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Works referenced in this record:
Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology
journal, April 2005
- Love, J. Christopher; Estroff, Lara A.; Kriebel, Jennah K.
- Chemical Reviews, Vol. 105, Issue 4
Electrochemical Stability of Self-Assembled Monolayers on Gold
journal, December 1998
- Beulen, Marcel W. J.; Kastenberg, Miryam I.; van Veggel, Frank C. J. M.
- Langmuir, Vol. 14, Issue 26
Free Energy and Temperature Dependence of Electron Transfer at the Metal-Electrolyte Interface
journal, February 1991
- Chidsey, C. E. D.
- Science, Vol. 251, Issue 4996
Attachment of organic layers to conductive or semiconductive surfaces by reduction of diazonium salts
journal, January 2005
- Pinson, Jean; Podvorica, Fetah
- Chemical Society Reviews, Vol. 34, Issue 5
Aryl diazonium salts: a new class of coupling agents for bonding polymers, biomacromolecules and nanoparticles to surfaces
journal, January 2011
- Mahouche-Chergui, Samia; Gam-Derouich, Sarra; Mangeney, Claire
- Chemical Society Reviews, Vol. 40, Issue 7
Electrocatalytic O 2 Reduction by Covalently Immobilized Mononuclear Copper(I) Complexes: Evidence for a Binuclear Cu 2 O 2 Intermediate
journal, March 2011
- McCrory, Charles C. L.; Devadoss, Anando; Ottenwaelder, Xavier
- Journal of the American Chemical Society, Vol. 133, Issue 11
Azide-Modified Graphitic Surfaces for Covalent Attachment of Alkyne-Terminated Molecules by “Click” Chemistry
journal, May 2007
- Devadoss, Anando; Chidsey, Christopher E. D.
- Journal of the American Chemical Society, Vol. 129, Issue 17
An Anodic Method for Covalent Attachment of Molecules to Electrodes through an Ethynyl Linkage
journal, February 2013
- Sheridan, Matthew V.; Lam, Kevin; Geiger, William E.
- Journal of the American Chemical Society, Vol. 135, Issue 8
Noncovalent Immobilization of Electrocatalysts on Carbon Electrodes for Fuel Production
journal, November 2013
- Blakemore, James D.; Gupta, Ayush; Warren, Jeffrey J.
- Journal of the American Chemical Society, Vol. 135, Issue 49
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
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
X-ray photoelectron spectra of inorganic molecules
journal, October 1981
- Brisdon, B. J.; Griffin, G. F.; Pierce, J.
- Journal of Organometallic Chemistry, Vol. 219, Issue 1
619. The polarographic reduction of pyridine, quinoline, and phenazine
journal, January 1952
- Kaye, R. C.; Stonehill, H. I.
- Journal of the Chemical Society (Resumed)
Electrochemistry of phenazine at a platinum electrode in aprotic solvents
journal, April 1972
- Sawyer, Donald T.; Komai, Ralph Y.
- Analytical Chemistry, Vol. 44, Issue 4
Donor-Dependent Kinetics of Interfacial Proton-Coupled Electron Transfer
journal, February 2016
- Jackson, Megan N.; Surendranath, Yogesh
- Journal of the American Chemical Society, Vol. 138, Issue 9
Water (in Water) as an Intrinsically Efficient Proton Acceptor in Concerted Proton Electron Transfers
journal, May 2011
- Bonin, Julien; Costentin, Cyrille; Louault, Cyril
- Journal of the American Chemical Society, Vol. 133, Issue 17
Electrochemical generation of a metal-hydride complex [(C5Me5)Ir(L) H]+ (L = 2,2′-bipyridine). The electrochemical behaviour.
journal, December 1993
- Caix, C.; Chardon-Noblat, S.; Deronzier, A.
- Journal of Electroanalytical Chemistry, Vol. 362, Issue 1-2
Electrochemical properties of [(C5Me5)RhIII(L)Cl]+ complexes (L = 2,2′-bipyridine or 1,10-phenanthroline derivatives) in solution in related polypyrrolic films. Application to electrocatalytic hydrogen generation
journal, June 1993
- Chardon-Noblat, Sylvie; Cosnier, Serge; Deronzier, Alain
- Journal of Electroanalytical Chemistry, Vol. 352, Issue 1-2
Synthesis and Characterization of Cationic Rhodium Peroxo Complexes
journal, October 2012
- Cipot-Wechsler, Judy; Covelli, Danielle; Praetorius, Jeremy M.
- Organometallics, Vol. 31, Issue 21
Reexamining Oxidation States during the Synthesis of 2-Rhodaoxetanes from Olefins
journal, December 2015
- Desnoyer, Addison N.; Behyan, Shirin; Patrick, Brian O.
- Inorganic Chemistry, Vol. 55, Issue 1
Immobilization and electrochemical properties of ruthenium and iridium complexes on carbon electrodes
journal, February 2016
- Gupta, Ayush; Blakemore, James D.; Brunschwig, Bruce S.
- Journal of Physics: Condensed Matter, Vol. 28, Issue 9
Coadsorption of ferrocene-terminated and unsubstituted alkanethiols on gold: electroactive self-assembled monolayers
journal, May 1990
- Chidsey, Christopher E. D.; Bertozzi, Carolyn R.; Putvinski, T. M.
- Journal of the American Chemical Society, Vol. 112, Issue 11, p. 4301-4306
Electron Transfer Kinetics of Tris(1,10-phenanthroline)ruthenium(II) Electrooxidation in Aprotic Solvents
journal, April 2000
- Winkler, Krzysztof; McKnight, Novelette; Fawcett, W. Ronald
- The Journal of Physical Chemistry B, Vol. 104, Issue 15
Photochemical Properties and Reactivity of a Ru Compound Containing an NAD/NADH-Functionalized 1,10-Phenanthroline Ligand
journal, February 2016
- Kobayashi, Katsuaki; Ohtsu, Hideki; Nozaki, Koichi
- Inorganic Chemistry, Vol. 55, Issue 5
Electrochemical parametrization of metal complex redox potentials, using the ruthenium(III)/ruthenium(II) couple to generate a ligand electrochemical series
journal, March 1990
- Lever, A. B. P.
- Inorganic Chemistry, Vol. 29, Issue 6, p. 1271-1285
Interfacial Electrochemistry
book, January 2010
- Schmickler, Wolfgang; Santos, Elizabeth
- Springer Berlin, Heidelberg
Works referencing / citing this record:
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journal, September 2019
- Wang, Jiong; Huang, Xiang; Xi, Shibo
- Angewandte Chemie International Edition, Vol. 58, Issue 38
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journal, June 2019
- Gu, Jun; Hsu, Chia-Shuo; Bai, Lichen
- Science, Vol. 364, Issue 6445
Linkage Effect in the Heterogenization of Cobalt Complexes by Doped Graphene for Electrocatalytic CO 2 Reduction
journal, August 2019
- Wang, Jiong; Huang, Xiang; Xi, Shibo
- Angewandte Chemie, Vol. 131, Issue 38
Heterogeneous molecular catalysts for electrocatalytic CO2 reduction
journal, May 2019
- Corbin, Nathan; Zeng, Joy; Williams, Kindle
- Nano Research, Vol. 12, Issue 9
Charge Transfer Modulated Activity of Carbon‐Based Electrocatalysts
journal, July 2019
- Tao, Li; Wang, Yuqing; Zou, Yuqin
- Advanced Energy Materials, Vol. 10, Issue 11
Designing materials for electrochemical carbon dioxide recycling
journal, July 2019
- Ross, Michael B.; De Luna, Phil; Li, Yifan
- Nature Catalysis, Vol. 2, Issue 8
Graphite-Conjugated Acids Reveal a Molecular Framework for Proton-Coupled Electron Transfer at Electrode Surfaces
journal, May 2019
- Jackson, Megan N.; Pegis, Michael L.; Surendranath, Yogesh
- ACS Central Science
Computational Insights on the Electrocatalytic Behavior of [Cp*Rh] Molecular Catalysts Immobilized on Graphene for Heterogeneous Hydrogen Evolution Reaction
text, January 2022
- Bani-Yaseen, Abdulilah Dawoud; Elbashier, Elkhansa
- Manara - Qatar Research Repository