In/Au(111)和Ir/Au(111)面上巴豆醛选择加氢的机理研究及比较

夏盛杰1 罗伟1 薛继龙1 孟跃1,2 蒋军辉1 倪哲明1

(1.浙江工业大学化学工程学院, 浙江杭州 310014)
(2.湖州师范学院生命科学学院, 浙江湖州 313000)

【摘要】基于巴豆醛在M/Au(111)合金表面(M=In,Ir)垂直吸附的最稳定吸附结构,采用密度泛函理论对其不完全加氢的反应机理进行探究。从不同加氢机理下各基元反应的活化能、反应热计算以及构型变化分析中可知,巴豆醛在M/Au(111)面上均优先对距离合金表面较近的C=O进行加氢,且以C为活性中心优先进行加氢为最优机理,其中第1步加氢反应的活化能较高,是该机理的控速步骤。反应物巴豆醛的O原子与合金的掺杂原子M形成较强的化学吸附,提高了M/Au(111)面对C=O加氢的选择性。巴豆醛按最优机理加氢的基元反应中在In/Au(111)面上最高反应能垒为0.969 e V,比在Ir/Au(111)面的最高反应能垒1.332 e V低,因此认为In/Au合金对其不完全加氢有更好的催化活性。

【关键词】 密度泛函理论; 巴豆醛; 计算化学; 加氢; 吸附; In/Au(111); Ir/Au(111);

【DOI】

【基金资助】 国家自然科学基金项目(21503188) supported by the National Natural Science Foundation of China(21503188) 浙江省自然科学基金项目(LQ15B030002) the Natural Science Foundation of Zhejiang Province(LQ15B030002)

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This Article

ISSN:0438-1157

CN: 11-1946/TQ

Vol 69, No. 04, Pages 1476-1483

April 2018

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Article Outline

摘要

  • 引言
  • 1 计算方法和模型
  • 2 结果与讨论
  • 3 结论
  • 符号说明
  • 参考文献