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Title: On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study

Abstract

The electro-oxidation of dimethyl ether (DME) was investigated using periodic, self-consistent density functional theory (DFT) calculations on the (111) and (100) facets of eight fcc metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh. The goal of this study is to understand the experimentally observed structure sensitivity of this reaction on Pt, and to predict trends in structure sensitivity of this reaction across the other seven metals studied. The main conclusion is that the enhanced activity of Pt(100) originates from more facile C–O bond breaking and removal of surface poisoning species, including CO and CH. When comparing C–O bond breaking energetics, we do not find a universal trend where these elementary steps are always more exergonic on the (100) facet. However, we find that, at a given potential, DME can be dehydrogenated (prior to breaking the C–O bond) to a greater extent on the (100) facet. Additionally, we find that the reaction energy for C–O bond breaking in CHxOCHy-type species becomes increasingly exergonic as the species becomes increasingly dehydrogenated. Together, the more facile dehydrogenation on the (100) facets provides more favorable routes to C–O bond activation. Though we calculate a lower onset potential on Au(100), Ag(100), Cu(100), Pt(100), andmore » Pd(100) than their respective (111) facets, the calculated onset potential for Ni(100), Ir(100), and Rh(100) are actually higher than for their respective (111) facets. Lastly, by constructing theoretical volcano plots, we conclude that Au(100), Ag(100), Cu(100), Pt(100), and Pd(100) should be more active than their respective (111) facets, while Ni(100), Rh(100), and Ir(100) will show the opposite trend.« less

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:
1405310
Grant/Contract Number:  
FG02-05ER15731
Resource Type:
Accepted Manuscript
Journal Name:
Topics in Catalysis
Additional Journal Information:
Journal Volume: 58; Journal Issue: 18-20; Journal ID: ISSN 1022-5528
Publisher:
Springer
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; dimethyl ether

Citation Formats

Herron, Jeffrey A., Ferrin, Peter, and Mavrikakis, Manos. On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study. United States: N. p., 2015. Web. doi:10.1007/s11244-015-0495-5.
Herron, Jeffrey A., Ferrin, Peter, & Mavrikakis, Manos. On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study. United States. doi:10.1007/s11244-015-0495-5.
Herron, Jeffrey A., Ferrin, Peter, and Mavrikakis, Manos. Thu . "On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study". United States. doi:10.1007/s11244-015-0495-5. https://www.osti.gov/servlets/purl/1405310.
@article{osti_1405310,
title = {On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study},
author = {Herron, Jeffrey A. and Ferrin, Peter and Mavrikakis, Manos},
abstractNote = {The electro-oxidation of dimethyl ether (DME) was investigated using periodic, self-consistent density functional theory (DFT) calculations on the (111) and (100) facets of eight fcc metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh. The goal of this study is to understand the experimentally observed structure sensitivity of this reaction on Pt, and to predict trends in structure sensitivity of this reaction across the other seven metals studied. The main conclusion is that the enhanced activity of Pt(100) originates from more facile C–O bond breaking and removal of surface poisoning species, including CO and CH. When comparing C–O bond breaking energetics, we do not find a universal trend where these elementary steps are always more exergonic on the (100) facet. However, we find that, at a given potential, DME can be dehydrogenated (prior to breaking the C–O bond) to a greater extent on the (100) facet. Additionally, we find that the reaction energy for C–O bond breaking in CHxOCHy-type species becomes increasingly exergonic as the species becomes increasingly dehydrogenated. Together, the more facile dehydrogenation on the (100) facets provides more favorable routes to C–O bond activation. Though we calculate a lower onset potential on Au(100), Ag(100), Cu(100), Pt(100), and Pd(100) than their respective (111) facets, the calculated onset potential for Ni(100), Ir(100), and Rh(100) are actually higher than for their respective (111) facets. Lastly, by constructing theoretical volcano plots, we conclude that Au(100), Ag(100), Cu(100), Pt(100), and Pd(100) should be more active than their respective (111) facets, while Ni(100), Rh(100), and Ir(100) will show the opposite trend.},
doi = {10.1007/s11244-015-0495-5},
journal = {Topics in Catalysis},
number = 18-20,
volume = 58,
place = {United States},
year = {2015},
month = {9}
}

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