Adsorption and Reaction of 1 -Epoxy-3-butene on Pt(111): Implications for Heterogeneous Catalysis of Unsaturated Oxygenates.
High-resolution electron energy loss spectroscopy (HREELS), temperature-programmed de- sorption (TPD), and density functional theory (DFT) calculations were used to study the adsorption and reaction of 1-epoxy-3-butene (EpB) on Pt(111). These investigations were conducted to help elucidate mechanism...
| Published in: | Journal of the American Chemical Society Vol. 130; no. 16; pp. 5507 - 5515 |
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| Main Authors: | , , |
| Format: | Article |
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American Chemical Society
4/23/2008
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| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=31880806&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 31880806 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 4/23/2008 vid: 130 iid: 16 pid: 997 pub: American Chemical Society artinfo: ui: 31880806 10.1021/ja711013n ppf: 5507 ppct: 8 formats: tig: atl: Adsorption and Reaction of 1 -Epoxy-3-butene on Pt(111): Implications for Heterogeneous Catalysis of Unsaturated Oxygenates. aug: au: Loh, Andrea S. Davis, Scott W. Medlin, J. Will affil: Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309-0424 su: Heterogeneous catalysis Butene Platinum Density functionals Adsorption (Chemistry) Chemical reactions Electron energy loss spectroscopy Thermal desorption sug: subj: Heterogeneous catalysis Butene Platinum Density functionals Adsorption (Chemistry) Chemical reactions Electron energy loss spectroscopy Thermal desorption ab: High-resolution electron energy loss spectroscopy (HREELS), temperature-programmed de- sorption (TPD), and density functional theory (DFT) calculations were used to study the adsorption and reaction of 1-epoxy-3-butene (EpB) on Pt(111). These investigations were conducted to help elucidate mechanisms for improving olefin hydrogenation selectivity in reactions of unsaturated oxygenates. EpB dosed to Pt(111) at 91 K adsorbs molecularly on the surface through the vinyl group with apparent rehybridization to a di-a-bound state. By 233 K, however, EpB undergoes epoxide ring opening to form an aldehyde intermediate, which further decomposes upon heating to yield gas phase products CO, H, and propylene. Comparison of the HREELS and TPD data to experiments performed with 2-butenal (crotonaldehyde) shows that EpB and 2-butenal decompose through related pathways. However, the EpB- derived aldehyde intermediate clearly has a unique structure, features of which have been elucidated by DFT calculations. In conjunction with previous surface science studies of EpB chemistry, these results can help explain selectivity trends for reactions of EpB on Pt catalysts and bimetallic PtAg catalysts, with indications that the enhanced olefin hydrogenation selectivity of PtAg catalysts likely originates from a bifunctional effect. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2008 holdings: @attributes: islocal: N |
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