caa a22 4500 606174443 CHVBK 20210128100738.0 cr unu---uuuuu 210128e20151101xx s 000 0 eng 10.1007/s11244-015-0495-5 doi (NATIONALLICENCE)springer-10.1007/s11244-015-0495-5 On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study [Elektronische Daten] [Jeffrey Herron, Peter Ferrin, Manos Mavrikakis] 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. Springer Science+Business Media New York, 2015 Density functional theory nationallicence Heterogeneous catalysis nationallicence Thermochemistry nationallicence Electrocatalysis nationallicence Oxidation nationallicence Dimethyl ether nationallicence Herron Jeffrey Department of Chemical and Biological Engineering, University of Wisconsin - Madison, 53706, Madison, WI, USA aut Ferrin Peter Department of Chemical and Biological Engineering, University of Wisconsin - Madison, 53706, Madison, WI, USA aut Mavrikakis Manos Department of Chemical and Biological Engineering, University of Wisconsin - Madison, 53706, Madison, WI, USA aut Topics in Catalysis Springer US; http://www.springer-ny.com 58/18-20(2015-11-01), 1159-1173 1022-5528 58:18-20<1159 2015 58 11244 https://doi.org/10.1007/s11244-015-0495-5 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s11244-015-0495-5 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Herron Jeffrey Department of Chemical and Biological Engineering, University of Wisconsin - Madison, 53706, Madison, WI, USA aut NATIONALLICENCE 700 1- Ferrin Peter Department of Chemical and Biological Engineering, University of Wisconsin - Madison, 53706, Madison, WI, USA aut NATIONALLICENCE 700 1- Mavrikakis Manos Department of Chemical and Biological Engineering, University of Wisconsin - Madison, 53706, Madison, WI, USA aut NATIONALLICENCE 773 0- Topics in Catalysis Springer US; http://www.springer-ny.com 58/18-20(2015-11-01), 1159-1173 1022-5528 58:18-20<1159 2015 58 11244