原子与分子物理学报Issue(1)：20-26,7.DOI:10.3969/j.issn.1000-0364.2016.02.004
2－丙醇和1，1，1－三氟－2－丙醇在Ni（100）表面的裂解机理
Decomposition mechanism of 2-propanol and 1,1,1-trifluoro-2-propanol on Ni(100) surface
摘要
Abstract
The possible decomposition mechanism of 2 -propanol and 1,1,1 -trifluoro -2 -propanol on Ni (100) surface was investigated utilizing the first -principles density functional theory (DFT) and self-consist-ent periodic calculation.The transition states were testified by using the complete Linear Synchronous Transit and the Quadratic Synchronous Transit ( LST/QST) methods.All the species involved in this process on three possi-ble adsorption sites (top, hollow, and bridge) on Ni(100) surface were fully optimized to obtain their equilibri-um geometries.The corresponding adsorption energies and Mullikan charge analysis of these species were predic -ted and compared.The favorable adsorption sites on Ni (100) surface for these species were found , respectively.The calculated results show that there are two parallel competitive dissociation processes of the β-hydrogen and theγ-hydrogen on Ni(100) surface for 2-propanol and 1,1,1-trifluoro-2-propanol, respectively.For the 2-propanol , in the β-hydrogen dissociation process , the barrier of rate -limiting step is 64.7 kJ · mol -1.However , the barrier of rate-limiting step is 233.1 kJ · mol -1 for the γ-hydrogen dissociation process , sug-gesting the superiority of β-hydrogen dissociation process.As a result, the main product is CH3 COCH3.On the contrary, for the 1,1,1-trifluoro-2-propanol, in the β-hydrogen dissociation process , the barrier of rate-limiting step is 257.1 kJ· mol-1.However, the barrier of rate-limiting step is 148.1 kJ· mol-1 for theγ-hy-drogen dissociation process , suggesting the superiority of γ-hydrogen dissociation process.As a result , the main product is CF3 CH=CH2.The results suggested that the decomposition mechanism of 2-propanol is changed by substituted at the γ-hydrogen with more electronegative fluorine atoms.It is found that the above mentioned the-oretical calculations agree well with the experiment results.关键词
2-丙醇/1,1,1-三氟-2-丙醇/Ni(100)表面/密度泛函理论Key words
2-propanol/1,1,1-trifluoro-2-propanol/Ni(100) surface/Density functional theory分类
化学化工引用本文复制引用
张福兰..2－丙醇和1，1，1－三氟－2－丙醇在Ni（100）表面的裂解机理[J].原子与分子物理学报,2016,(1):20-26,7.基金项目
重庆市教委科学技术资助项目 （）
