Complete H-D Exchange of Butene via D Absorbed in a Pd-Au Alloy
Complete H-D Exchange of Butene via D Absorbed in a Pd-Au Alloy
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DOI：
10.1021/acs.jpcc.5b07216
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发表时间：
2015-10-22
影响因子：
3.7
通讯作者：
Fukutani, Katsuyuki
中科院分区：
文献类型：
--
作者：
Ogura, Shohei;Okada, Michio;Fukutani, Katsuyuki
H-D交换反应是合成含氚化合物最简单的方法之一。烯烃在钯、铂等金属表面的H-D交换已被广泛研究。然而，丁烯在这些表面上的H-D交换很难完成，总是伴随着加氢或脱氢，其反应机理尚不清楚。在本研究中，我们用热脱附光谱(TDS)、反射红外光谱(RAIRS)和TDS模拟研究了顺丁烯和1-丁烯与吸附在Pd70Au30(110)近表面区域的H和D原子的反应。我们发现丁烯同分异构体完全氢-D交换，没有氢化和脱氢。两种丁烯异构体相似的产物产率分布表明，在该表面上有快速的双西格玛键迁移，这是完成H-D交换的关键。我们的结果将有助于理解和控制Pd-Au合金和Pd相关表面的催化活性和选择性，并将开辟结合吸氢和合金化表面的新化学。
The H-D exchange reaction is one of the easiest ways to synthesize deuterium-labeled compounds. H-D exchange of olefins has been widely studied on metal surfaces such as Pd and Pt. However, H-D exchange of butene on these surfaces is hardly completed and always accompanied by hydrogenation or dehydrogenation, and its reaction mechanism is yet to be elucidated. In the present study, we investigated the reaction of cis-2- and 1-butenes with H and D atoms absorbed in the near-surface region of Pd70Au30(110) by using thermal desorption spectroscopy (TDS), reflection absorption infrared spectroscopy (RAIRS), and TDS simulation. We show complete H-D exchange of both butene isomers without hydrogenation and dehydrogenation. Similar product yield distributions for both butene isomers indicate a fast di-sigma bond migration on this surface, which is a key for the complete H-D exchange. Our results would lead to understanding and controlling the catalytic activity and selectivity of the Pd-Au alloy and Pd-related surfaces and would open up a new chemistry using absorbed hydrogen in combination with alloyed surfaces.