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Title: Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals

Abstract

We studied here the thermodynamic isotope effects (TIEs) and kinetic isotope effects (KIEs) for H2/D2 dissociative adsorption using periodic, density functional theory (DFT)-based calculations. We examined the TIEs on the close-packed, open, and stepped surfaces, of twelve transition metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Re, Ir, Pt, and Au), and the KIEs on the surfaces of three noble metals (Cu, Ag, and Au). Both TIEs and KIEs were evaluated at 1/9 ML coverage. We find distinct TIEs on different adsorption sites, indicating that TIEs could be used in conjunction with binding energies to determine the dominant adsorption sites for hydrogen. Additionally, we find that while H2 dissociative adsorption may traditionally be considered structure insensitive in terms of reaction rates, it can exhibit structure sensitivity in terms of its KIEs. Complementarily to TIEs, KIEs might therefore be useful for identifying active sites for H2 dissociative adsorption on the three noble metal transition metal catalysts studied.

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1494809
Alternate Identifier(s):
OSTI ID: 1454279
Grant/Contract Number:  
FG02-05ER15731; AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 8; Journal Issue: 13; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bai, Yunhai, Chen, Benjamin W. J., Peng, Guowen, and Mavrikakis, Manos. Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals. United States: N. p., 2018. Web. doi:10.1039/C8CY00878G.
Bai, Yunhai, Chen, Benjamin W. J., Peng, Guowen, & Mavrikakis, Manos. Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals. United States. doi:10.1039/C8CY00878G.
Bai, Yunhai, Chen, Benjamin W. J., Peng, Guowen, and Mavrikakis, Manos. Wed . "Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals". United States. doi:10.1039/C8CY00878G. https://www.osti.gov/servlets/purl/1494809.
@article{osti_1494809,
title = {Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals},
author = {Bai, Yunhai and Chen, Benjamin W. J. and Peng, Guowen and Mavrikakis, Manos},
abstractNote = {We studied here the thermodynamic isotope effects (TIEs) and kinetic isotope effects (KIEs) for H2/D2 dissociative adsorption using periodic, density functional theory (DFT)-based calculations. We examined the TIEs on the close-packed, open, and stepped surfaces, of twelve transition metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Re, Ir, Pt, and Au), and the KIEs on the surfaces of three noble metals (Cu, Ag, and Au). Both TIEs and KIEs were evaluated at 1/9 ML coverage. We find distinct TIEs on different adsorption sites, indicating that TIEs could be used in conjunction with binding energies to determine the dominant adsorption sites for hydrogen. Additionally, we find that while H2 dissociative adsorption may traditionally be considered structure insensitive in terms of reaction rates, it can exhibit structure sensitivity in terms of its KIEs. Complementarily to TIEs, KIEs might therefore be useful for identifying active sites for H2 dissociative adsorption on the three noble metal transition metal catalysts studied.},
doi = {10.1039/C8CY00878G},
journal = {Catalysis Science and Technology},
number = 13,
volume = 8,
place = {United States},
year = {2018},
month = {6}
}

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Figure 1 Figure 1: Top views of high symmetry adsorption sites for atomic hydrogen on (a) hcp(0001), (b) bcc(110), (c) fcc(111), (d) fcc(100), and (e) fcc(211) surfaces. Filled circles denote the surface atoms, and open circles denote high symmetry sites. Atoms in light purple (in (e)) highlight the step edge.

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    Works referencing / citing this record:

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    • Chen, Benjamin W. J.; Mavrikakis, Manos
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