Organosulfur chemistry on W(211) surfaces. 1. A comparison of methanethiol and methanol
The reactions of methanol and methanethiol on clean, oxided, sulfided, and carbided W(211) surfaces were studied by LEED, AES, and TPR. Adsorption occurred by an oxidative addition in which the hydroxyl or sulfhydryl hydrogen was removed forming methoxy and methanethioxy intermediates. Clean W(211) was a very strong reductant totally decomposing the molecules. Adsorbed oxygen oxidized the surface making it a weaker reducing agent so that alkoxy and thioxy intermediates were stabilized. An epitaxial surface oxide was a mild oxidant compared to clean W(211); this surface oxidized methanol to formaldehyde. Adsorbed sulfur severely reduced methanol adsorption. Surfaces with adsorbed sulfur adsorbed methanethiol. This adsorption suggests the formation of disulfide species. Carbided W(211) stabilized both alkoxy and thioxy intermediates as well as oxidizing methanol to formaldehyde. The adsorbed methoxy and methanethioxy intermediates decomposed by C-O or C-S bond scission forming adsorbed methyl groups which either decomposed or were hydrogenated to form methane. At temperatures above 500 K methyl groups recombined and C2 hydrocarbon products evolved. Surface oxides and carbides oxidized methoxy to formaldehyde and CO, but no surface oxidized methanethioxy to thioformaldehyde or CS. 38 references, 8 figures, 5 tables.
- Research Organization:
- Princeton Univ., NJ
- OSTI ID:
- 6301657
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 89:23; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ADSORPTION
ADSORPTION HEAT
ALKANES
CARBIDES
CARBON COMPOUNDS
CATALYSIS
CHALCOGENIDES
CHEMICAL REACTIONS
COHERENT SCATTERING
CRYSTALS
DATA
DIFFRACTION
ELECTRON DIFFRACTION
ELECTRON SPECTROSCOPY
ELEMENTS
ENTHALPY
EXPERIMENTAL DATA
FORMATION HEAT
HYDROCARBONS
INFORMATION
MEDIUM TEMPERATURE
METALS
METHANE
MONOCRYSTALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
REACTION HEAT
REFRACTORY METAL COMPOUNDS
SCATTERING
SORPTION
SPECTROSCOPY
SULFIDES
SULFUR COMPOUNDS
SURFACE PROPERTIES
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
TUNGSTEN
TUNGSTEN CARBIDES
TUNGSTEN COMPOUNDS
TUNGSTEN OXIDES
TUNGSTEN SULFIDES