物理化学学报Issue(8)：1456-1464,9.DOI:10.3866/PKU.WHXB201406091
Au（111）面上肉桂醛的选择性加氢机理
Selective Hydrogenation Mechanism of Cinnamaldehyde on Au(111) Surface
肖雪春 1施炜 1倪哲明1
作者信息
- 1. 浙江工业大学化学工程学院，先进催化材料实验室，杭州310032
- 折叠
摘要
Abstract
The adsorption behavior and selective hydrogenation reaction mechanisms (C=O addition, C=C addition, and 1,4-conjugate addition) of cinnamaldehyde on an Au(111) surface were investigated by density functional theory combined with a periodic slab model. The adsorption energies of various adsorption models were obtained to determine the preferred adsorption configuration. The calculated results indicate that the most stable adsorption configuration involved the C=O and C=C double bond adsorbed on the Au(111) surface, with an average adsorption energy of 140.0 kJ∙mol-1. The transition states of each elementary reaction for al possible reaction mechanisms were also located. Comparison of the activation energy barriers revealed hydrocinnamaldehyde (HCAL) to be the most likely selective hydrogenation product of cinnamaldehyde on an Au(111) surface. In addition, the 1,4-conjugate addition mechanism, which generates 3-phenyl-1-propen-1-ol (ENOL) that readily tautomerizes to HCAL, required less activation energy than did the C=C direct addition mechanism. The dominant reaction pathway involved an O atom of cinnamaldehyde preferential y hydrogenating to generate a more stable al yl intermediate. Another H atom then added to a C atom directly connected to the phenyl ring of the al yl intermediate to yield ENOL. Final y, ENOL tautomerized to HCAL. Throughout the process, the generation of ENOL is the rate-determining step, for which the highest activation energy barrier was required.关键词
Au(111)面/肉桂醛/密度泛函理论/苯丙醛/选择性加氢机理Key words
Au(111) surface/Cinnamaldehyde/Density functional theory/Hydrocinnamaldehyde/Selective hydrogenation mechanism分类
化学化工引用本文复制引用
肖雪春,施炜,倪哲明..Au（111）面上肉桂醛的选择性加氢机理[J].物理化学学报,2014,(8):1456-1464,9.
