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

Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos

doi:10.1021/jp512981f

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

Journal Article · Fri Feb 20 00:00:00 EST 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp512981f· OSTI ID:1405312

Herron, Jeffrey A. ^[1]; Ferrin, Peter ^[2]; Mavrikakis, Manos ^[2]

Univ. of Wisconsin-Madison, Madison, WI (United States). Dept. of Chemical and Biological Engineering; Department of Chemical and Biological Engineering, University of Wisconsin−Madison
Univ. of Wisconsin-Madison, Madison, WI (United States). Dept. of Chemical and Biological Engineering

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 NH₃ electro-oxidation.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin-Madison, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Contributing Organization:: EMSL, a National scientific user facility at Pacific Northwest National Laboratory (PNNL); and the National Energy Research Scientific Computing Center (NERSC); the Center for Nanoscale Materials at Argonne National Laboratory (ANL)

Grant/Contract Number:: FG02-05ER15731

OSTI ID:: 1405312

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 26 Vol. 119; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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

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