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권영국

Kwon, Youngkook
Electrochemistry Lab for Energy and Environment
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Why (100) Terraces Break and Make Bonds: Oxidation of Dimethyl Ether on Platinum Single-Crystal Electrodes

Author(s)
Li, HongjiaoCalle-Vallejo, FedericoKolb, Manuel J.Kwon, YoungkookLi, YongdanKoper, Marc T. M.
Issued Date
2013-09
DOI
10.1021/ja406655q
URI
https://scholarworks.unist.ac.kr/handle/201301/26538
Fulltext
https://pubs.acs.org/doi/10.1021/ja406655q
Citation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.135, no.38, pp.14329 - 14338
Abstract
A surface structural preference for (1 0 0) terraces of fcc metals is displayed by many bond-breaking or bond-making reactions in electrocatalysis. Here, this phenomenon is explored in the electrochemical oxidation of dimethyl ether (DME) on platinum. The elementary C-O bond-breaking step is identified and clarified by combining information obtained from single-crystal experiments and density functional theory (DFT) calculations. Experiments on Pt(1 0 0), Pt(5 1 0), and Pt(10 1 0) surfaces show that the surface structure sensitivity is due to the bond-breaking step, which is unfavorable on step sites. DFT calculations suggest that the precursor for the bond-breaking step is a CHOC adsorbate that preferentially adsorbs on a square ensemble of four neighboring atoms on Pt(1 0 0) terraces, named as "the active site". Step sites fail to strongly adsorb CHOC and are, therefore, ineffective in breaking C-O bonds, resulting in a decrease in activity on surfaces with increasing step density. Our combined experimental and computational results allow the formulation of a new mechanism for the electro-oxidation of DME as well as a simple general formula for the activity of different surfaces toward electrocatalytic reactions that prefer (1 0 0) terrace active sites.
Publisher
AMER CHEMICAL SOC
ISSN
0002-7863
Keyword
AUGMENTED-WAVE METHODACID-SOLUTIONSETHANOL ELECTROOXIDATIONALKALINE-SOLUTIONSURFACE-STRUCTUREOXYGEN REDUCTIONFUEL-CELLCOADSORPTIONPT(100)

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