Topics in Catalysis

, Volume 58, Issue 18–20, pp 1159–1173 | Cite as

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

  • Jeffrey A. Herron
  • Peter Ferrin
  • Manos Mavrikakis
Original Paper

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), 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. Finally, 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.

Keywords

Density functional theory Heterogeneous catalysis Thermochemistry Electrocatalysis Oxidation Dimethyl ether 

Notes

Acknowledgments

Prof. Vayenas has inspired many colleagues in the field of electrocatalysis, including these authors. We wish him the best on the occasion of his 65th birthday. This work was supported by DOE-BES, Office of Chemical Sciences. JAH thanks Air Products & Chemicals, Inc. for partial support through a graduate fellowship. Computational work was performed in part using supercomputing resources at the following institutions: 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). EMSL is sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL. CNM, and NERSC are supported by the U.S. Department of Energy, Office of Science, under contracts DE-AC02-06CH11357, and DE-AC02-05CH11231, respectively.

Supplementary material

11244_2015_495_MOESM1_ESM.docx (4.1 mb)
Supplementary material 1 (DOCX 4172 kb)

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Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Jeffrey A. Herron
    • 1
  • Peter Ferrin
    • 1
  • Manos Mavrikakis
    • 1
  1. 1.Department of Chemical and Biological EngineeringUniversity of Wisconsin – MadisonMadisonUSA

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