Actions for Mechanistic Study of Nitric Oxide Reduction by Hydrogen on Pt(100) (I) [electronic resource] : A DFT Analysis of the Reaction Network

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Mechanistic Study of Nitric Oxide Reduction by Hydrogen on Pt(100) (I) [electronic resource] : A DFT Analysis of the Reaction Network

Published
Washington, D.C. : United States. Dept. of Energy. Office of Basic Energy Sciences, 2017.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
Physical Description
pages 432-443 : digital, PDF file
Additional Creators
University of Wisconsin, United States. Department of Energy. Office of Basic Energy Sciences, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
Periodic, self-consistent density functional theory (DFT-GGA, PW91) calculations are used to study the reaction mechanism for nitric oxide (NO) reduction by hydrogen (H2) on Pt(100). Energetics of various N–O activation paths, including both direct and hydrogen-assisted N–O bond-breaking paths, and the formation of three different N-containing products (N2, N2O, and NH3), are systematically studied. On the basis of our analysis, NO* dissociation has a lower barrier than NO* hydrogenation to HNO* or NOH*, and therefore, the direct NO dissociation path is predicted to dominate N–O activation on clean Pt(100). The reaction of atomic N* with N* and NO* is proposed as the mechanism for N2 and N2O formation, respectively. NH3 formation from N* via three successive hydrogenation steps is also studied and is found to be kinetically more difficult than N2 and N2O formation from N*. Finally, NO adsorption phase diagrams on Pt(100) are constructed, and these phase diagrams suggest that, at low temperatures (e.g., 400 K), the Pt(100) surface may be covered by half a monolayer of NO. We propose that high NO coverage might affect the NO + H2 reaction mechanism, and therefore, one should explicitly take the NO coverage into consideration in first-principles studies to determine the reaction mechanism on catalyst surfaces under reaction conditions. In conclusion, a detailed analysis of high NO coverage effects on the reaction mechanism will be presented in a separate contribution.
Report Numbers
E 1.99:1397268
Subject(s)
Note
Published through SciTech Connect.
05/08/2017.
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry 122 2 ISSN 1520-6106 AM
Yunhai Bai; Manos Mavrikakis.
Funding Information
FG02-05ER15731
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