肉桂醛在M_(13)(M=Au,Pt)团簇表面加氢反应机理分析  

Hydrogenation mechanisms of cinnamaldehyde over M_(13)(M=Au,Pt) clusters

作　　者：曹根庭[1] 薛继龙[2] 肖雪春[2] 倪哲明[2] 

机构地区：[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

出　　处：《化工学报》2016年第4期1333-1339,共7页CIESC Journal

基　　金：浙江省自然科学基金项目(LQ15B030002)~~

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M_(13)(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Au_(13)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Pt_(13)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。The selective hydrogenation reaction mechanisms（C=O addition mechanism, C=C addition mechanism, and 1,4-conjugate addition mechanism） of cinnamaldehyde over M（13）（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 Au（13） 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 Pt（13） 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.

关 键 词：肉桂醛 M13团簇 密度泛函理论 加氢 

分 类 号：O641[理学—物理化学]