Unusual Selectivity of Gold Catalysts for Hydrogenation of 1,3-Butadiene toward cis-2-Butene: A Joint Experimental and Theoretical Investigation
Unusual Selectivity of Gold Catalysts for Hydrogenation of 1,3-Butadiene toward cis-2-Butene: A Joint Experimental and Theoretical Investigation
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金催化剂对 1,3-丁二烯加氢生成顺-2-丁烯的异常选择性：实验和理论联合研究
DOI：
10.1021/jp9107415
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发表时间：
2010-01
影响因子：
3.7
通讯作者：
Wang, Ai-Qin
中科院分区：
文献类型：
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作者：
Yang, Xiao-Feng;Zhang, Tao;Li, Jun;Wang, Yi-Lei;Wang, Ai-Qin
我们报告了一个结合实验和理论研究的不寻常的催化性能的金纳米粒子在1，3-丁二烯的选择性加氢。结果发现，纳米金催化剂表现出独特的偏好形成顺式-2-丁烯相比，反式异构体，顺式/反式异构体的比例是结构敏感的金纳米粒子的大小。我们的密度泛函理论计算表明，顺式-1，3-丁二烯可以更好地吸附在金纳米粒子的边缘和角落相比，反式-1，3-丁二烯。此外，过渡态计算表明，反式丁二烯异构化为顺式丁二烯的动力学是有利的，具有相当低的能量障碍。基于轨道相互作用分析，讨论了金纳米粒子对1，3-丁二烯吸附的这些独特性质。研究发现，由于空间匹配，Au-6s分子轨道优先吸附顺式-1，3-丁二烯而非反式异构体。C...
We report a combined experimental and theoretical investigation of the unusual catalytic properties of gold nanoparticles in the selective hydrogenation of 1,3-butadiene. It is found that nanogold catalysts exhibit a unique preference toward forming cis-2-butene compared to the trans isomer, and the ratio of cis/trans isomers is structure-sensitive in terms of the size of gold nanoparticles. Our density functional theory calculations show that the cis-1,3-butadiene can be preferably adsorbed at the edges and corners of gold nanoparticles as compared to the trans-1,3-butadiene. Moreover, the transition state calculations indicate that the isomerization of trans-butadiene to cis-butadiene is kinetically favorable, with rather low energy barriers. These unique properties of gold nanoparticles toward 1,3-butadiene adsorption are discussed based on orbital interaction analyses. It is found that Au-6s-based molecular orbitals prefer adsorption of cis-1,3-butadiene to the trans isomer due to spatial match. The c...