催化学报

催化学报 ›› 2012, Vol. 33 ›› Issue (10): 1706-1711.DOI: 10.3724/SP.J.1088.2012.20617

• 研究论文 • 上一篇    下一篇

Rh(111) 及 Rh@Cu(111) 表面乙烯氢甲酰化反应选择性的理论研究

马秀芳, 赵永慧, 苏海燕, 李微雪*   

  1. 中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连 116023
  • 收稿日期:2012-06-15 修回日期:2012-07-16 出版日期:2012-09-28 发布日期:2012-09-28

Theoretical Study of Selectivity of Ethylene Hydroformylation on Rh(111) and Rh@Cu(111) Surfaces

MA Xiufang, ZHAO Yonghui, SU Haiyan, LI Weixue*   

  1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
  • Received:2012-06-15 Revised:2012-07-16 Online:2012-09-28 Published:2012-09-28

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756

被引次数

4

摘要： 采用密度泛函理论对比研究了 Rh(111) 表面与 Rh@Cu(111) 表面合金上乙基加氢反应及 CO 插入反应过程. 结果发现, 与 Rh(111) 表面相比, Rh@Cu(111) 表面合金的集团效应和配体效应使得加氢反应的能垒降低了 0.12 eV, 而 CO 插入反应的却显著降低了 0.78 eV. 这表明 RhCu 合金催化剂可以有效地提高氢甲酰化反应的选择性.

关键词: 氢甲酰化, 铑, 铜, 合金, 密度泛函理论

Abstract: Selectivity-determining steps for ethylene hydroformylation, i.e., ethyl hydrogenation versus CO insertion on Rh(111) and Rh@Cu(111) surfaces were investigated by density functional theory calculations. Compared with the Rh(111) surface, the Rh@Cu(111) surface decreases the hydrogenation barrier by 0.12 eV and more significantly the CO insertion barrier by 0.78 eV due to the ensemble and ligand effects. This result indicates that Rh@Cu(111) alloy catalyst can improve the selectivity of the hydroformylation.

Key words: hydroformylation, rhodium, copper, alloy, density functional theory