au（111）面上肉桂醛的选择性加氢机理.pdf

1456物理化学学~(WuliHuaxueXuebao),30(8),1456-1464August[Article】doi:(111)面上肉桂醛的选择性加氢机理肖雪春施炜倪哲明(浙江工业大学化学工程学院,先进催化材料实验室,杭州310032)摘要:采用密度泛函理论并结合周期性平板模型的方法,优化了肉桂醛在Au(111)面上的吸附模型,并详细探讨了肉桂醛在Au(111)面上选择性加氢的反应机理(C=O,C:C以及1,4共轭加成机理).计算结果表明,肉桂醛以C=O和C=C协同吸附于Au(111)面上时,,‘mol~.通过搜索不同机理下每个基元反应的过渡态,得出肉桂醛在Au(111)面上最可能的选择性加氢产物为苯丙醛,且其按照1,4共轭加成机理间接得到苯丙醛比C=:肉桂醛C=O的O优先加H形成烯丙基型中间体,继而该中间体中与苯环相连的C原子继续加H形成烯醇(ENOL),,:Au(111)面:肉桂醛:密度泛函理论:苯丙醛:选择性加氢机理中图分类号:O641SelectiveHydrOgenationMechanismofCinnamaldehydeonAu(111)SurfaceXIAOXue—ChunSHIWeiNIZhe—Ming(LaboratoryofAdvancedCatalyticMaterials,CollegeofChemicalEngineering,Zh~iangUniversityofTechnology,Hangzhou310032,:Theadsorptionbehaviorandselectivehydrogenationreactionmechanisms(C=Oaddition,C=Caddition,and1,4-conjugateaddition)ofcinnamaldehydeonanAu(111)=OandC=CdoublebondadsorbedontheAu(111)surface,·mol~.parisonoftheactivationenergYbarriersrevealedhydrocinnamaldehyde(HCAL)tobethemostIikelyselectivehydrogenationproductofcinnamaldehydeonanAu(111),the1,4-conjugateadditionmechanism,(ENOL)thatreadily