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 Title: Stepped single crystals as improved model for supported catalysts: Ethylene, methanol and assorted molecules on platinum(511) and platinum(331) Author(s): Spaendonk, Vincent Van Department / Program: Chemical and Biomolecular Engineering Discipline: Chemical Engineering Degree Granting Institution: University of Illinois at Urbana-Champaign Degree: Ph.D. Genre: Dissertation Subject(s): Chemistry, Physical Engineering, Chemical Physics, Condensed Matter Abstract: Past research has shown unusual activity of the (1 x 1)Pt(110) surface to break carbon-carbon and carbon-oxygen bonds. Methane formation from ethylene or ethane has been reported for supported platinum catalysts. A model for the methane formation on (1 x 1)Pt(110), was proposed by Yagasaki. In this study, the mechanism of methane formation has been further investigated, and Yagasaki's model tested, by studying the decomposition of ethylene and methanol on the stepped surfaces Pt(511) and Pt(331) with Temperature Programmed Desorption. The experiments have been carried out in a Ultra High Vacuum system, equipped with a mass spectrometer, LEED and AES. Hydrogen and carbon monoxide desorption show that on Pt(511) different adsorption sites are available than on Pt(331). Ethylene decomposition on Pt(511) leads to small amounts of methane formation compared to (1 x 1)Pt(110). The metastable (1 x 1) phase of Pt(511) is 2-3 times more active than the stable (hex) phase. When $\rm\sp{13}C\sb2H\sb4$ is used, $\rm\sp{13}CH\sb4$ is not detected. Methane formation is not seen on the Pt(331) surface. Arguments are given why Pt(511) is a superior model for supported catalysts compared to (1 x 1)Pt(110). The carbon-oxygen bond of methanol is not broken on either Pt(511) or Pt(331), whether the surface is clean or covered with oxygen. Hydrogen saturating the surface, prevents the chemisorption of ethylene and the formation of methane. Postadsorption of hydrogen does not lead to an increase in methane formation. Coadsorption of ethylene with carbon monoxide shows a maximum methane formation at 0.3 L carbon monoxide exposure. Poison experiments with 'oxide' and carbon indicate that the active site for methane formation is located at the step. The amount of carbon deposited during ethylene decomposition, increases in the order (1 x 1)Pt(511) $\to$ (hex)Pt(511) $\to$ Pt(331). This is also the order for decreasing methane activity. In a new model, it is proposed that in order to be active for methane formation, a surface has to prevent the polymerization of single carbon species to inactive graphite. The model predicts that surfaces with large enough (111) terraces have higher diffusion rates and allow the single carbon species to convert to graphite before the species can be hydrogenated. Issue Date: 1994 Type: Text Language: English URI: http://hdl.handle.net/2142/21509 Rights Information: Copyright 1994 Spaendonk, Vincent Van Date Available in IDEALS: 2011-05-07 Identifier in Online Catalog: AAI9512557 OCLC Identifier: (UMI)AAI9512557
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