Selective blocking of active sites on supported gold catalysts by adsorbed thiols and its effect on the catalytic behavior: A combined experimental and theoretical study

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• 作者：Peter Haider ; Atsushi Urakawa ; Erik Schmidt ; Alfons Baiker
• 关键词：Gold ; Hydrogenation of ketopantolactone ; Oxidation of benzyl alcohol ; Selective poisoning ; Site blocking ; Thiols
• 刊名：Journal of Molecular Catalysis A: Chemical
• 出版年：2009
• 出版时间：15 June 2009
• 年：2009
• 卷：305
• 期：1-2
• 页码：161-169
• 全文大小：1019 K

文摘

Selective blocking (poisoning) of catalytic active sites of gold catalysts, CeO₂ and TiO₂ supported Au colloids (2.1 and 6.9 nm), was investigated in the aerobic oxidation of benzyl alcohol as well as in the hydrogenation of ketopantolactone by adding various amounts of two chemically distinct thiols with different functionalities (n-octadecanethiol, ODT, and mercaptoacetic acid, MAA). There were clear trends in their poisoning behaviors, independent of the type of support and Au particle size. ODT poisoned the catalyst in the oxidation reaction much stronger than MAA. In contrast, MAA was a stronger poisoning agent in the hydrogenation reaction. The characteristics of supported Au particles and the nature of thiol adsorption were investigated by Attenuated Total Reflection Infrared (ATR-IR) spectroscopy, TEM, thermogravimetric desorption and DFT calculations. Based on the adsorption characteristics of two thiols derived from the combined experimental and theoretical study, it is suggested that CO hydrogenation of ketopantolactone occurs preferentially at low coordination sites such as corners and edges, which are more dominant in small clusters, while oxidation seems to be favored on extended active sites as prevailing on larger Au clusters.