Petrochemical Research Institute, Lanzhou Petrochemical Research Center, PetroChina Company Limited, Lanzhou, 730060, China,
J Mol Model. 2013 Nov;19(11):4789-95. doi: 10.1007/s00894-013-1954-1. Epub 2013 Sep 8.
We have theoretically investigated the adsorption of thiophene, benzothiophene, dibenzothiophene on Na(I)Y and rare earth exchanged La(III)Y, Ce(III)Y, Pr(III)Y Nd(III)Y zeolites by density functional theory calculations. The calculated results show that except benzothiophene adsorbed on Na(I)Y with a stand configuration, the stable adsorption structures of other thiophenic compounds on zeolites exhibit lying configurations. Adsorption energies of thiophenic compounds on the Na(I)Y are very low, and decrease with the increase of the number of benzene rings in thiophenic compounds. All rare earth exchanged zeolites exhibit strong interaction with thiophene. La(III)Y and Nd(III)Y zeolites are found to show enhanced adsorption energies to benzothiophene and Pr(III)Y zeolites are favorable for dibenzothiophene adsorption. The analysis of the electronic total charge density and electron orbital overlaps show that the thiophenic compounds interact with zeolites by π-electrons of thiophene ring and exchanged metal atom. Mulliken charge populations analysis reveals that adsorption energies are strongly dependent on the charge transfer of thiophenic molecule and exchanged metal atom.
我们通过密度泛函理论计算理论研究了噻吩、苯并噻吩、二苯并噻吩在 Na(I)Y 和稀土交换的 La(III)Y、Ce(III)Y、Pr(III)Y、Nd(III)Y 沸石上的吸附。计算结果表明，除了噻吩在 Na(I)Y 上以直立构型吸附外，其他噻吩类化合物在沸石上的稳定吸附结构均呈现躺卧构型。噻吩类化合物在 Na(I)Y 上的吸附能非常低，且随噻吩类化合物中环数的增加而降低。所有稀土交换沸石都与噻吩表现出很强的相互作用。La(III)Y 和 Nd(III)Y 沸石对苯并噻吩表现出增强的吸附能，而 Pr(III)Y 沸石有利于二苯并噻吩的吸附。电子总电荷密度和电子轨道重叠的分析表明，噻吩类化合物通过噻吩环的π电子和交换金属原子与沸石相互作用。Mulliken 电荷布居分析表明，吸附能强烈依赖于噻吩分子和交换金属原子的电荷转移。
