A vibrational and TDS study of sulfur adsorbates on Cu(100): Evidence for CH3S species

Vibrational (EELS) and TDS data for methyl mercaptan (CH₃SH), dimethyl sulfide (CH₃)₂S and dimethyl disulfide (CH₃S)₂ are analyzed to determine the nature of the adsorption states on Cu(100). Dimethyl sulfide is reversibly adsorbed on Cu(100); no dissociation (CS bond breaking) was found. By contrast, methyl mercaptan and dimethyl disulfide dissociate below 300 K to form adsorbed CH₃S (methyl mercaptide) species. Depending on the coverage, two orientations of methyl mercaptide are found: linear and bent. The two different orientations can be distinguished via the surface dipole selection rule by different intensities of the methyl rocking and deformation vibrations. By contrast with the methoxy species, which on Cu(100) decomposes to formaldehyde, no H₂C=S is liberated during decomposition of CH₃S. The mercaptide is stable to ∼ 350 K, but decomposes at higher temperatures to form adsorbed sulfur and recombinant methane, hydrogen and ethane. The methane appears to be formed by methyl-hydrogen recombination when the C-S bond scission occurs. TDS results show that sulfur released from the decomposition poisons the surface toward further adsorption. In addition, the selectivity toward methane versus ethane can be altered by pre-titrating the adsorbed hydrogen with oxygen, thereby changing the relative methyl-hydrogen and methyl-methyl recombination probabilities.