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Title: 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:
 [1];  [2];  [3];  [4];  [5]
  1. Univ. of Illinois-Champaign, Urbana, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States); Leiden Univ., Leiden (The Netherlands)
  2. Leiden Univ., Leiden (The Netherlands); Shandong Jianzhu Univ., Jinan (People's Republic of China)
  3. Univ. of Illinois-Champaign, Urbana, IL (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States)
  5. 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. https://doi.org/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 = {2016},
month = {1}
}

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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
  • DOI: 10.1021/cr8003696

On the use of ammonia electrolysis for hydrogen production
journal, March 2005


Electro-oxidation of ammonia in waste water
journal, July 1978

  • Marinčić, L.; Leitz, F. B.
  • Journal of Applied Electrochemistry, Vol. 8, Issue 4
  • DOI: 10.1007/BF00612687

Electrochemical oxidation of ammonia in alkaline solutions: its application to an amperometric sensor
journal, January 1998


DEMS-cyclic voltammetry investigation of the electrochemistry of nitrogen compounds in 0.5 M potassium hydroxide
journal, January 1994


A DEMS and cyclic voltammetry study of NH3 oxidation on platinized platinum
journal, May 1998


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
  • DOI: 10.1016/S0022-0728(01)00491-0

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
  • DOI: 10.1139/v63-243

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
  • DOI: 10.1016/S0022-0728(70)80103-6

Selective electrocatalysis of ammonia oxidation on Pt(100) sites in alkaline medium
journal, January 2003


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
  • DOI: 10.1021/jp051269d

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
  • DOI: 10.1016/j.jelechem.2006.01.009

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
  • DOI: 10.1039/b601306f

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
  • DOI: 10.1021/ja508649p

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
  • DOI: 10.1021/ja8032185

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
  • DOI: 10.1021/ja203234v

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
  • DOI: 10.1021/cs4002404

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
  • DOI: 10.1021/ja406655q

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
  • DOI: 10.1016/S0022-0728(84)80090-X

The influence of pH on the reduction of CO and CO 2 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
  • DOI: 10.1016/j.jelechem.2013.08.033

Theory of the transition from sequential to concerted electrochemical proton–electron transfer
journal, January 2013


Theory of multiple proton–electron transfer reactions and its implications for electrocatalysis
journal, January 2013


Volcano Activity Relationships for Proton-Coupled Electron Transfer Reactions in Electrocatalysis
journal, September 2015


On the behavior of the Pt(100) and vicinal surfaces in alkaline media
journal, December 2011


Electrochemistry of Pt (100) in alkaline media: A voltammetric study
journal, October 2010


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
  • DOI: 10.1016/0022-0728(92)80323-V

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
  • DOI: 10.1021/jp064742b

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
  • DOI: 10.1039/c1cp21717h

Nitric oxide adsorption at Pt(100) electrode surfaces
journal, November 1998


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
  • DOI: 10.1021/jp4048874

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
  • DOI: 10.1021/jp512981f

Theoretical study of ammonia oxidation on platinum clusters – Adsorption of ammonia and water fragments
journal, June 2012


Theoretical study of ammonia oxidation on platinum clusters – Adsorption of intermediate nitrogen dimer molecules
journal, July 2013


    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
    • DOI: 10.1002/aenm.201800369

    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
    • DOI: 10.1149/2.0431815jes

    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
    • DOI: 10.1039/c6sc02984a