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Enhancement of selective decomposition. Adsorption and reaction of methanethiol on carbon-covered W(001)

Journal Article · · Journal of Physical Chemistry
;  [1]
  1. Oak Ridge National Lab., TN (United States)

Selective decomposition of methanethiol (CH{sub 3}SH) on carbon-covered W(001) to produce methane is enhanced by 75% compared to the clean surface. The maximum enhancement requires only 0.25 monolayers (ML) of preadsorbed C. On a surface percovered with 0.8 ML of C, the methane desorbs in peaks at 460 and 550 K compared to 360 K on the clean surface, suggesting a greater stability in the C-S and C-H bonds. Increased intramolecular bond stability is confirmed by the temperature dependence of the S 2p and C 1s soft X-ray photoemission. Methyl thiolate, CH{sub 3}S, forms upon adsorption at 100 K. Chemisorbed methanethiol, which is not stable on the clean surface, is also observed between 100 and 300 K. The chemisorbed thiol decomposes to form additional thiolate. The thiolate reacts along three competing pathways. It undergoes rehydrogenation and desorbs as methanethiol, it selectively decomposes to form desorbed methane and adsorbed S, or it totally decomposes to form S, C, and desorbed H{sub 2}. 23 refs., 11 figs., 1 tab.

Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-84OR21400; AC02-76CH00016
OSTI ID:
41839
Journal Information:
Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 15 Vol. 99; ISSN JPCHAX; ISSN 0022-3654
Country of Publication:
United States
Language:
English

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