Surface electrochemistry of CO on Pt(111): Anion Effects

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In-situ studies of CO adsorption by surface x-ray scattering (SXS) and Fourier transform infrared (FTIR) spectroscopy techniques are used to create the link between the macroscopic kinetic rates of CO oxidation and the microscopic level of understanding the structure/site occupancy of CO on Pt(111). A remarkable difference in activity was observed between alkaline and acid solutions. In alkaline solution the oxidation of CO proceeds at low overpotential (<0.2 V) by the surface reaction between the adsorbed CO and OH, the latter forming selectively in the hydrogen underpotential potential region at defect sites. In acid solution these sites are blocked by ... continued below

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Markovic, N.M.; Lucas, C.A.; Rodes, A.; Stamenkovic, V. & Ross, P.N. July 30, 2001.

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In-situ studies of CO adsorption by surface x-ray scattering (SXS) and Fourier transform infrared (FTIR) spectroscopy techniques are used to create the link between the macroscopic kinetic rates of CO oxidation and the microscopic level of understanding the structure/site occupancy of CO on Pt(111). A remarkable difference in activity was observed between alkaline and acid solutions. In alkaline solution the oxidation of CO proceeds at low overpotential (<0.2 V) by the surface reaction between the adsorbed CO and OH, the latter forming selectively in the hydrogen underpotential potential region at defect sites. In acid solution these sites are blocked by specific adsorption of anions, and consequently in a solution containing Br{sup -} the ignition potential is shifted positively by 0.6 V. Anions of supporting electrolytes also have dramatic effects on both the potential range of stability and the domain size of the p(2x2)-3CO structure which is formed at 0.05 V. The stability/domain size of this structure increases from KOH (ca. 30 {angstrom} between 0.05 < E < 0.3V), to HClO{sub 4} (ca. 140 {angstrom} between 0.05 < E < 0.6V) to HClO{sub 4} + Br{sup -} (ca 350 {angstrom} between 0.05 < E < 0.8V). The larger the ordered domains of the p(2x2)-CO{sub ad} structure are, the less active the surface is towards CO oxidation.

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  • Journal Name: Surface Science Letters; Journal Volume: 499; Journal Issue: 2-3; Related Information: Journal Publication Date: 03/01/2002

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  • Report No.: LBNL--48684
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 861157
  • Archival Resource Key: ark:/67531/metadc786314

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  • July 30, 2001

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  • Dec. 3, 2015, 9:30 a.m.

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  • April 1, 2016, 8:18 p.m.

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Markovic, N.M.; Lucas, C.A.; Rodes, A.; Stamenkovic, V. & Ross, P.N. Surface electrochemistry of CO on Pt(111): Anion Effects, article, July 30, 2001; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc786314/: accessed October 21, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.