Evidence for decoupled electron and proton transfer in the electrochemical oxidation of ammonia on Pt(100)
Abstract
The two traditional mechanisms of the electrochemical ammonia oxidation consider only concerted proton-electron transfer elementary steps and thus they predict that the rate–potential relationship is independent of the pH on the pH-corrected RHE potential scale. In this letter we show that this is not the case: the increase of the solution pH shifts the onset of the NH3-to-N2 oxidation on Pt(100) to lower potentials and also leads to higher surface concentration of formed NOad before the latter is oxidized to nitrite. Therefore, we present a new mechanism for the ammonia oxidation which incorporates a deprotonation step occurring prior to the electron transfer. The deprotonation step yields a negatively charged surface-adsorbed species which is discharged in a subsequent electron transfer step before the N–N bond formation. The negatively charged species is thus a precursor for the formation of N2 and NO. The new mechanism should be a future guide for computational studies aiming at the identification of intermediates and corresponding activation barriers for the elementary steps. As a result, ammonia oxidation is a new example of a bond-forming reaction on (100) terraces which involves decoupled proton-electron transfer.
- Authors:
-
- Univ. of Illinois-Champaign, Urbana, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States); Leiden Univ., Leiden (The Netherlands)
- Leiden Univ., Leiden (The Netherlands); Shandong Jianzhu Univ., Jinan (People's Republic of China)
- Univ. of Illinois-Champaign, Urbana, IL (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Leiden Univ., Leiden (The Netherlands)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1248379
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 3; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- ammonia oxidation; bond-forming reactions; nitrogen cycle; pH effects; sequential proton-electron transfer
Citation Formats
Katsounaros, Ioannis, Chen, Ting, Gewirth, Andrew A., Markovic, Nenad M., and Koper, Marc T. M. Evidence for decoupled electron and proton transfer in the electrochemical oxidation of ammonia on Pt(100). United States: N. p., 2016.
Web. doi:10.1021/acs.jpclett.5b02556.
Katsounaros, Ioannis, Chen, Ting, Gewirth, Andrew A., Markovic, Nenad M., & Koper, Marc T. M. Evidence for decoupled electron and proton transfer in the electrochemical oxidation of ammonia on Pt(100). United States. https://doi.org/10.1021/acs.jpclett.5b02556
Katsounaros, Ioannis, Chen, Ting, Gewirth, Andrew A., Markovic, Nenad M., and Koper, Marc T. M. Tue .
"Evidence for decoupled electron and proton transfer in the electrochemical oxidation of ammonia on Pt(100)". United States. https://doi.org/10.1021/acs.jpclett.5b02556. https://www.osti.gov/servlets/purl/1248379.
@article{osti_1248379,
title = {Evidence for decoupled electron and proton transfer in the electrochemical oxidation of ammonia on Pt(100)},
author = {Katsounaros, Ioannis and Chen, Ting and Gewirth, Andrew A. and Markovic, Nenad M. and Koper, Marc T. M.},
abstractNote = {The two traditional mechanisms of the electrochemical ammonia oxidation consider only concerted proton-electron transfer elementary steps and thus they predict that the rate–potential relationship is independent of the pH on the pH-corrected RHE potential scale. In this letter we show that this is not the case: the increase of the solution pH shifts the onset of the NH3-to-N2 oxidation on Pt(100) to lower potentials and also leads to higher surface concentration of formed NOad before the latter is oxidized to nitrite. Therefore, we present a new mechanism for the ammonia oxidation which incorporates a deprotonation step occurring prior to the electron transfer. The deprotonation step yields a negatively charged surface-adsorbed species which is discharged in a subsequent electron transfer step before the N–N bond formation. The negatively charged species is thus a precursor for the formation of N2 and NO. The new mechanism should be a future guide for computational studies aiming at the identification of intermediates and corresponding activation barriers for the elementary steps. As a result, ammonia oxidation is a new example of a bond-forming reaction on (100) terraces which involves decoupled proton-electron transfer.},
doi = {10.1021/acs.jpclett.5b02556},
journal = {Journal of Physical Chemistry Letters},
number = 3,
volume = 7,
place = {United States},
year = {Tue Jan 12 00:00:00 EST 2016},
month = {Tue Jan 12 00:00:00 EST 2016}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 47 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Nitrogen Cycle Electrocatalysis
journal, June 2009
- Rosca, Victor; Duca, Matteo; de Groot, Matheus T.
- Chemical Reviews, Vol. 109, Issue 6
On the use of ammonia electrolysis for hydrogen production
journal, March 2005
- Vitse, Frédéric; Cooper, Matt; Botte, Gerardine G.
- Journal of Power Sources, Vol. 142, Issue 1-2
Electro-oxidation of ammonia in waste water
journal, July 1978
- Marinčić, L.; Leitz, F. B.
- Journal of Applied Electrochemistry, Vol. 8, Issue 4
Electrochemical oxidation of ammonia in alkaline solutions: its application to an amperometric sensor
journal, January 1998
- de Mishima, B. A. López; Lescano, D.; Holgado, T. Molina
- Electrochimica Acta, Vol. 43, Issue 3-4
DEMS-cyclic voltammetry investigation of the electrochemistry of nitrogen compounds in 0.5 M potassium hydroxide
journal, January 1994
- Wasmus, S.; Vasini, E. J.; Krausa, M.
- Electrochimica Acta, Vol. 39, Issue 1
A DEMS and cyclic voltammetry study of NH3 oxidation on platinized platinum
journal, May 1998
- Gootzen, J. F. E.; Wonders, A. H.; Visscher, W.
- Electrochimica Acta, Vol. 43, Issue 12-13
The role of adsorbates in the electrochemical oxidation of ammonia on noble and transition metal electrodes
journal, June 2001
- de Vooys, A. C. A.; Koper, M. T. M.; van Santen, R. A.
- Journal of Electroanalytical Chemistry, Vol. 506, Issue 2
The Anodic Oxidation of Ammonia at Platinum Black Electrodes in Aqueous koh Electrolyte
journal, July 1963
- Oswin, H. G.; Salomon, M.
- Canadian Journal of Chemistry, Vol. 41, Issue 7
Untersuchungen Zur anodischen Oxidation von Ammoniak an Platin-Elektroden
journal, May 1970
- Gerischer, H.; Mauerer, A.
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 25, Issue 3
Selective electrocatalysis of ammonia oxidation on Pt(100) sites in alkaline medium
journal, January 2003
- Vidal-Iglesias, F. J.; Garcı́a-Aráez, N.; Montiel, V.
- Electrochemistry Communications, Vol. 5, Issue 1
Ammonia Selective Oxidation on Pt(100) Sites in an Alkaline Medium
journal, July 2005
- Vidal-Iglesias, Francisco J.; Solla-Gullón, José; Montiel, Vicente
- The Journal of Physical Chemistry B, Vol. 109, Issue 26
DEMS study of ammonia oxidation on platinum basal planes
journal, March 2006
- Vidal-Iglesias, F. J.; Solla-Gullón, J.; Feliu, J. M.
- Journal of Electroanalytical Chemistry, Vol. 588, Issue 2
Electrocatalytic oxidation of ammonia on Pt(111) and Pt(100) surfaces
journal, January 2006
- Rosca, Victor; Koper, Marc T. M.
- Physical Chemistry Chemical Physics, Vol. 8, Issue 21
Bond-Making and Breaking between Carbon, Nitrogen, and Oxygen in Electrocatalysis
journal, October 2014
- Li, Hongjiao; Li, Yongdan; Koper, Marc T. M.
- Journal of the American Chemical Society, Vol. 136, Issue 44
Unique Activity of Platinum Adislands in the CO Electrooxidation Reaction
journal, November 2008
- Strmcnik, Dusan S.; Tripkovic, Dusan V.; van der Vliet, Dennis
- Journal of the American Chemical Society, Vol. 130, Issue 46
Selective Catalytic Reduction at Quasi-Perfect Pt(100) Domains: A Universal Low-Temperature Pathway from Nitrite to N 2
journal, July 2011
- Duca, Matteo; Figueiredo, Marta C.; Climent, Victor
- Journal of the American Chemical Society, Vol. 133, Issue 28
Structure Sensitivity of the Electrochemical Reduction of Carbon Monoxide on Copper Single Crystals
journal, April 2013
- Schouten, Klaas Jan P.; Pérez Gallent, Elena; Koper, Marc T. M.
- ACS Catalysis, Vol. 3, Issue 6
Why (1 0 0) Terraces Break and Make Bonds: Oxidation of Dimethyl Ether on Platinum Single-Crystal Electrodes
journal, September 2013
- Li, Hongjiao; Calle-Vallejo, Federico; Kolb, Manuel J.
- Journal of the American Chemical Society, Vol. 135, Issue 38
Structural effects in electrocatalysis
journal, May 1984
- Adić, R. R.; Marković, N. M.; Vešović, V. B.
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 165, Issue 1-2
The influence of pH on the reduction of CO and to hydrocarbons on copper electrodes
journal, March 2014
- Schouten, Klaas Jan P.; Pérez Gallent, Elena; Koper, Marc T. M.
- Journal of Electroanalytical Chemistry, Vol. 716
Theory of the transition from sequential to concerted electrochemical proton–electron transfer
journal, January 2013
- Koper, Marc T. M.
- Phys. Chem. Chem. Phys., Vol. 15, Issue 5
Theory of multiple proton–electron transfer reactions and its implications for electrocatalysis
journal, January 2013
- Koper, Marc T. M.
- Chemical Science, Vol. 4, Issue 7
Volcano Activity Relationships for Proton-Coupled Electron Transfer Reactions in Electrocatalysis
journal, September 2015
- Koper, Marc T. M.
- Topics in Catalysis, Vol. 58, Issue 18-20
On the behavior of the Pt(100) and vicinal surfaces in alkaline media
journal, December 2011
- Arán-Ais, Rosa M.; Figueiredo, Marta C.; Vidal-Iglesias, Francisco J.
- Electrochimica Acta, Vol. 58
Electrochemistry of Pt (100) in alkaline media: A voltammetric study
journal, October 2010
- van der Vliet, Dennis F.; Koper, Marc T. M.
- Surface Science, Vol. 604, Issue 21-22
Mechanistic Similarity in Catalytic N 2 Production from NH 3 and NO 2 – at Pt(100) Thin Films: Toward a Universal Catalytic Pathway for Simple N-Containing Species, and Its Application to in Situ Removal of NH 3 Poisons
journal, April 2015
- Finkelstein, David A.; Bertin, Erwan; Garbarino, Sébastien
- The Journal of Physical Chemistry C, Vol. 119, Issue 18
Hydrogen adsorption on single-crystal platinum electrodes in alkaline solutions
journal, July 1992
- Marinković, N. S.; Marković, N. M.; Adz̆ić, R. R.
- Journal of Electroanalytical Chemistry, Vol. 330, Issue 1-2
Ammonia Dehydrogenation over Platinum-Group Metal Surfaces. Structure, Stability, and Reactivity of Adsorbed NH x Species
journal, January 2007
- Novell-Leruth, Gerard; Valcárcel, Ana; Pérez-Ramírez, Javier
- The Journal of Physical Chemistry C, Vol. 111, Issue 2
Near-surface ion distribution and buffer effects during electrochemical reactions
journal, January 2011
- Auinger, Michael; Katsounaros, Ioannis; Meier, Josef C.
- Physical Chemistry Chemical Physics, Vol. 13, Issue 36
Nitric oxide adsorption at Pt(100) electrode surfaces
journal, November 1998
- Rodes, A.; Climent, V.; Orts, J. M.
- Electrochimica Acta, Vol. 44, Issue 6-7
Combined First-Principles Molecular Dynamics/Density Functional Theory Study of Ammonia Electrooxidation on Pt(100) Electrode
journal, November 2013
- Skachkov, Dmitry; Venkateswara Rao, Chitturi; Ishikawa, Yasuyuki
- The Journal of Physical Chemistry C, Vol. 117, Issue 48
Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study
journal, February 2015
- Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos
- The Journal of Physical Chemistry C, Vol. 119, Issue 26
Theoretical study of ammonia oxidation on platinum clusters – Adsorption of ammonia and water fragments
journal, June 2012
- Daramola, Damilola A.; Botte, Gerardine G.
- Computational and Theoretical Chemistry, Vol. 989
Theoretical study of ammonia oxidation on platinum clusters – Adsorption of intermediate nitrogen dimer molecules
journal, July 2013
- Daramola, Damilola A.; Botte, Gerardine G.
- Journal of Colloid and Interface Science, Vol. 402
Works referencing / citing this record:
A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions
journal, May 2018
- Cui, Xiaoyang; Tang, Cheng; Zhang, Qiang
- Advanced Energy Materials, Vol. 8, Issue 22
The Direct Ammonia Fuel Cell and a Common Pattern of Electrocatalytic Processes
journal, January 2018
- Gottesfeld, Shimshon
- Journal of The Electrochemical Society, Vol. 165, Issue 15
Proton-coupled electron transfer in the electrocatalysis of CO 2 reduction: prediction of sequential vs. concerted pathways using DFT
journal, January 2017
- Göttle, Adrien J.; Koper, Marc T. M.
- Chemical Science, Vol. 8, Issue 1