期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 135, 期 38, 页码 14329-14338出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja406655q
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资金
- Chinese Scholarship Council (CSC) through a CSC Scholarship
- Netherlands Organization for Scientific Research (NWO)
- National Research School Combination Catalysis (NRSC-C, The Netherlands)
- Smart Mix Program of The Netherlands Ministry of Economic Affairs
- NWO
- Natural Science Foundation of China [21120102039]
- Netherlands Ministry of Education, Culture and Science
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.
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