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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (9): 1028-1036. 上一篇    下一篇

研究论文

Pd(Cu)在MgO(100)表面吸附CO和O2的理论研究

郝兰，王艳*，陈光巨*   

  1. 北京师范大学化学学院 北京 100875
  • 投稿日期:2007-05-07 修回日期:2007-09-27 发布日期:2008-05-14
  • 通讯作者: 王艳

Theoretical Study on the Adsorption of CO and O2 on MgO-Supported Pd and Cu Atoms

HAO Lan WANG Yan* CHEN Guang-Ju*   

  1. (College of Chemistry, Beijing Normal University, Beijing 100875, China)
  • Received:2007-05-07 Revised:2007-09-27 Published:2008-05-14
  • Contact: Wang Yan

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采用固体镶嵌势能模型和DFT/B3LYP方法研究了在Pd/MgO和Cu/MgO表面吸附CO和O2分子的电子性质. 计算结果表明, 在完美MgO(100)表面Pd原子对CO和O2的吸附能分别为206.5和84.8 kJ/mol, 因此可知Pd原子更容易吸附CO分子; 而当Pd原子附着于有氧缺陷的MgO表面时, 它对两种分子的吸附都非常弱. 相反, 附着于MgO表面的Cu原子对O2分子的吸附更为有利, 其吸附能在140～155 kJ/mol之间. 研究结果还表明, 对于双分子吸附体系, 即CO＋CO, CO＋O2, O2＋O2体系, 双分子之间的结合力可减小完美MgO表面上Pd原子与被吸附分子的相互作用, 使吸附能减少了46～96 kJ/mol. 而对于在MgO表面上的Cu原子, 只有O2＋O2 体系使吸附能减少了大约50～71 kJ/mol.

关键词: DFT/B3LYP, 团簇镶嵌模型, Pd(Cu)/MgO表面, 缺陷, CO/O2吸附

The physical properties of adsorption and co-adsorption properties of CO and O2 molecules on the MgO-supported Pd and Cu atoms have been studied at the DFT/B3LYP level of theory using the embedded cluster model. The calculations show that the supported Pd atom on the perfect surface is energetically more favorable for adsorbing a CO molecule than an O2 molecule, with the respective binding energies of 206.5 vs. 84.8 kJ/mol. While such interactions on Pd atom located above an oxygen vacancy of the MgO(100) surface are very weak, due to significant amount of electron charge transferring from the vacancy to Pd atom. In contrast, the supported Cu atom on both types of surfaces prefers to adsorb O2 molecule, instead of CO molecule, with the O2 binding energies of 140～155 kJ/mol. It was found that the binding between the two-coadsorbates for CO＋CO, CO＋O2, O2＋O2 coadsorbed on the supported Pd atom on the perfect surface reduced the admolecule-Pd interactions by the reductive energies of 46～96 kJ/mol. Such reductions only for O2＋O2 coadsorbed on the supported Cu atom on both surfaces are considerable with the reductive energies of 50～71 kJ/mol.

Key words: DFT/B3LYP method, embedded cluster model, Pd(Cu)/MgO surface, oxygen vacancy, CO/O2 adsorption and coadsorption