Site requirements for the reactions of CH₃SH and (CH₃)₂S₂ on ZnO()

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• 作者：B. Halevi ; John M. Vohs
• 关键词：Thermal desorption spectroscopy ; Surface chemical reaction ; Zinc oxide ; Low index single crystal surfaces
• 刊名：Surface Science
• 出版年：2008
• 期刊代码：104_00396028
• 类别：ch
• 出版时间：1 January 2008
• 卷：602
• 期：1
• 页码：198-204
• 文件大小：660 K

摘要

Temperature programmed desorption (TPD) was used to investigate the adsorption and reaction of CH₃SH and (CH₃)₂S₂ on the nonpolar () surface of ZnO. Methanethiol was found to dissociate on the (c35a23fce75353c744c40d">) surface to produce adsorbed methylthiolates. The primary reaction pathways for the methylthiolates were methyl group transfer between adjacent thiolates to produce (CH₃)₂S at 510 K, and transfer of methyl groups to surface lattice oxygen to produce adsorbed methoxides which were oxidized to CH₂O at 525 K and adsorbed formate. Dimethyldisulfide was found to dissociate via cleavage of the S–S bond to form adsorbed methylthiolates. The reaction pathways for thiolates produced in this manner were similar to those produced from CH₃SH except for an additional low-temperature pathway for the production of CH₂O. Comparison of the results obtained in this study to our previous study of the reaction of CH₃SH and (CH₃)₂S₂ on ZnO(0 0 0 1) and published STM studies of ZnO() and ZnO(0 0 0 1) indicates that step edges are the active sites for the reaction of thiols and disulfides on these surfaces.