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Title: Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study

Abstract

Here, we investigate the catalytic electro-oxidation of ammonia on model close-packed surfaces of Au, Ag, Cu, Pd, Pt, Ni, Ir, Co, Rh, Ru, Os, and Re to derive insights for the reaction mechanism and evaluate the catalysts based on their energy efficiency and activity in the context of their application in fuel cells. Two mechanisms, which are differentiated by their N–N bond formation step, are compared: (1) a mechanism proposed by Gerischer and Mauerer, whereby the N–N bond formation occurs between hydrogenated NH x adsorbed species, and (2) a mechanism in which N–N bond formation occurs between N adatoms. The results of our study show that the mechanism proposed by Gerischer and Mauerer is kinetically preferred and that the formation of N adatoms poisons the surface of the catalyst. On the basis of a simple Sabatier analysis, we predict that Pt is the most active monometallic catalyst followed by Ir and Cu, whereas all other metal surfaces studied here have significantly lower activity. We conclude by outlining some design principles for bimetallic alloy catalysts for NH 3 electro-oxidation.

Authors:
 [1];  [1];  [1]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
Univ. of Wisconsin-Madison, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
EMSL, a National scientific user facility at Pacific Northwest National Laboratory (PNNL); the Center for Nanoscale Materials at Argonne National Laboratory (ANL); and the National Energy Research Scientific Computing Center (NERSC)
OSTI Identifier:
1405312
Grant/Contract Number:  
FG02-05ER15731
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 26; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; density functional theory; heterogeneous catalysis; thermochemistry; electrocatalysis; oxidation; ammonia

Citation Formats

Herron, Jeffrey A., Ferrin, Peter, and Mavrikakis, Manos. Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study. United States: N. p., 2015. Web. doi:10.1021/jp512981f.
Herron, Jeffrey A., Ferrin, Peter, & Mavrikakis, Manos. Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study. United States. doi:10.1021/jp512981f.
Herron, Jeffrey A., Ferrin, Peter, and Mavrikakis, Manos. Fri . "Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study". United States. doi:10.1021/jp512981f. https://www.osti.gov/servlets/purl/1405312.
@article{osti_1405312,
title = {Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study},
author = {Herron, Jeffrey A. and Ferrin, Peter and Mavrikakis, Manos},
abstractNote = {Here, we investigate the catalytic electro-oxidation of ammonia on model close-packed surfaces of Au, Ag, Cu, Pd, Pt, Ni, Ir, Co, Rh, Ru, Os, and Re to derive insights for the reaction mechanism and evaluate the catalysts based on their energy efficiency and activity in the context of their application in fuel cells. Two mechanisms, which are differentiated by their N–N bond formation step, are compared: (1) a mechanism proposed by Gerischer and Mauerer, whereby the N–N bond formation occurs between hydrogenated NHx adsorbed species, and (2) a mechanism in which N–N bond formation occurs between N adatoms. The results of our study show that the mechanism proposed by Gerischer and Mauerer is kinetically preferred and that the formation of N adatoms poisons the surface of the catalyst. On the basis of a simple Sabatier analysis, we predict that Pt is the most active monometallic catalyst followed by Ir and Cu, whereas all other metal surfaces studied here have significantly lower activity. We conclude by outlining some design principles for bimetallic alloy catalysts for NH3 electro-oxidation.},
doi = {10.1021/jp512981f},
journal = {Journal of Physical Chemistry. C},
number = 26,
volume = 119,
place = {United States},
year = {2015},
month = {2}
}

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Cited by: 11 works
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