肉桂醛在M13(M=Au,Pt)团簇表面加氢反应机理分析

doi:10.11949/j.issn.0438-1157.20151297

化工学报 ›› 2016, Vol. 67 ›› Issue (4): 1333-1339.DOI: 10.11949/j.issn.0438-1157.20151297

• 催化、动力学与反应器 • 上一篇下一篇

肉桂醛在M₁₃(M=Au,Pt)团簇表面加氢反应机理分析

曹根庭¹, 薛继龙², 肖雪春², 倪哲明²

1. 浙江海洋学院海洋科学与技术学院, 浙江舟山 316004;
2. 浙江工业大学化学工程学院, 浙江杭州 310014

收稿日期:2015-08-12 修回日期:2015-11-24 出版日期:2016-04-05 发布日期:2016-04-05
通讯作者: 倪哲明
基金资助:
浙江省自然科学基金项目(LQ15B030002)。

Hydrogenation mechanisms of cinnamaldehyde over M₁₃(M=Au, Pt) clusters

CAO Genting¹, XUE Jilong², XIAO Xuechun², NI Zheming²

1. Marine Science and Technology College, Zhejiang Ocean University, Zhoushan 316004, Zhejiang, China;
2. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2015-08-12 Revised:2015-11-24 Online:2016-04-05 Published:2016-04-05
Supported by:
supported by the Natural Science Foundation of Zhejiang Province(LQ15B030002).

摘要/Abstract

摘要：

采用密度泛函理论系统地研究了肉桂醛在正二十面体M₁₃(M=Au,Pt)团簇上的选择性加氢反应机理(C=O,C=C以及1,4共轭加成机理)。在稳定吸附构型的基础上,通过Complete LST/QST方法探索肉桂醛选择性加氢反应中各基元反应的过渡态,得到各反应的活化能和反应热。计算结果表明:肉桂醛在Au₁₃团簇最可能发生1,4共轭加成得到烯醇,但烯醇很不稳定,会发生异构生成苯丙醛,反应总体放出热量;肉桂醛在Pt₁₃团簇最可能发生C=O加成得到肉桂醇,肉桂醇进一步加氢得到饱和醇,反应总体吸收热量。

关键词: 肉桂醛, M₁₃团簇, 密度泛函理论, 加氢

Abstract:

The selective hydrogenation reaction mechanisms (C=O addition mechanism, C=C addition mechanism, and 1,4-conjugate addition mechanism) of cinnamaldehyde over M₁₃(M=Au, Pt) were investigated using density functional theory. The transition states of each elementary reaction step in selective hydrogenation of cinnamaldehyde were explored by the complete LST/QST method on the basis of optimized stable adsorption configurations, hence the activation energy and reaction heat were obtained. The calculation results showed that on Au₁₃ cluster, cinnamaldehyde most likely follows 1,4-conjugate addition mechanism to produce very unstable ENOL, and tautomerizes to benzenepropanal(HCAL), of which the total hydrogenation process is almost exothermic. However, on Pt₁₃ cluster, it most likely follows the C=O addition mechanism to generate cinnamyl alcohol(COL) followed by further hydrogenation to saturated alcohols, of which the total hydrogenation process is almost endothermic.

Key words: cinnamaldehyde, M₁₃ cluster, density functional theory, hydrogenation

中图分类号:

O641

曹根庭, 薛继龙, 肖雪春, 倪哲明. 肉桂醛在M₁₃(M=Au,Pt)团簇表面加氢反应机理分析[J]. 化工学报, 2016, 67(4): 1333-1339.

CAO Genting, XUE Jilong, XIAO Xuechun, NI Zheming. Hydrogenation mechanisms of cinnamaldehyde over M₁₃(M=Au, Pt) clusters[J]. CIESC Journal, 2016, 67(4): 1333-1339.

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肉桂醛在M₁₃(M=Au,Pt)团簇表面加氢反应机理分析

Hydrogenation mechanisms of cinnamaldehyde over M₁₃(M=Au, Pt) clusters

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