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• W1964126827 endingPage "260" @default.
• W1964126827 startingPage "246" @default.
• W1964126827 abstract "The reactivity of Pt(100) towards methanol depends on surface structure and the nature and amount of coadsorbed reaction modifiers. We studied the adsorption and reaction of CH3OH in ultrahigh vacuum on the clean hex and (1 × 1) surfaces of Pt(100) and with coadsorbed O, Bi, and CO with thermal desorption spectroscopy and high resolution electron energy loss spectroscopy. Methanol adsorbs molecularly on Pt(100) at 100 K and decomposes to adsorbed H and CO in the temperature range of 170–220 K. The vibrational spectra show evidence for surface interactions involving both the hydroxyl (O-H … Pt) and methyl (C-H … Pt) hydrogens of molecular methanol. Under static conditions (no desorption of reaction products) as much as 0.085 ± 0.01 monolayers of methanol react on the clean hex surface. Chemical saturation of the surface, which occurs when the total coverage of surface reaction products reaches about one-half of a monolayer, limits the maximum extent of reaction on the hex, (1 × 1), and O-covered surfaces. The (1 × 1) surface enhances methanol reaction by factors of 1–3.4 compared to reaction following the same exposure on the hex surface. Reaction with preadsorbed oxygen leads to a methoxy intermediate (CH3O) and enhancement factors of 1–2.5 for oxygen coverages below 0.15 and above 0.3 monolayers. Coadsorbed oxygen enhances methanol reaction stoichiometrically, by scavenging H atoms to form OH and H2O, and nonstoichiometrically, most likely by local lifting of the hex reconstruction. Oxygen coverages between 0.15 and 0.3 monolayers inhibit the reaction by factors of 1—0.85 through blocking of reactive sites. Both Bi and CO inhibit the reaction by factors of 1—0.05 through a combination of ensemble and site blocking effects. Methanol decomposition requires an ensemble of 5 adsorption sites, as determined by Bi coadsorption experiments. The adsorbate/substrate combinations in this study represent model electrochemical situations, and we briefly discuss the implications of these findings toward methanol electrocatalysis." @default.
• W1964126827 created "2016-06-24" @default.
• W1964126827 creator A5048124333 @default.
• W1964126827 creator A5074871353 @default.
• W1964126827 date "1993-05-01" @default.
• W1964126827 modified "2023-10-16" @default.
• W1964126827 title "Promotion and poisoning of the reaction of methanol on clean and modified platinum (100)" @default.
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• W1964126827 doi "https://doi.org/10.1016/0039-6028(93)90409-d" @default.
• W1964126827 hasPublicationYear "1993" @default.
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