H2O2[Hnmp]HCOO氧化苯并噻吩类硫化物的量子化学研究
摘要：摘要针对质子型离子液体[Hnmp]HCOO在加入H2O2后生成的过氧化物[Hnmp]HCOOO氧化苯并噻吩（BT）、二苯并噻吩（DBT）和4,6-二甲基二苯并噻吩（4,6-DMDBT）的氧化脱硫反应，采用密度泛函理论DFT/B3LYP-D3方法考察了这三种硫化物的反应历程。首先通过几何优化得到了[Hnmp]HCOO和[Hnmp]HCOOO的稳定结构，然后考察了[Hnmp]HCOOO氧化BT、DBT和4,6-DMDBT的反应机理，寻找可能的过渡态、中间体，计算各步反应的能量变化。结果表明，[Hnmp]HCOOO先将硫化物氧化成亚砜，然后进一步氧化成砜；在氧化过程中，DBT的反应速率是三者中最快的，与文献的实验结果一致，且H2O2/[Hnmp]HCOO体系的脱硫效果优于传统的H2O2/HCOOH体系。
Abstract:：In this work, the oxidative desulfurization (ODS) mechanisms of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) in [Hnmp]HCOO ionic liquid with H2O2 as oxidant were studied by density functional theory DFT/B3LYP-D3 method. Firstly, the most stable structures of [Hnmp]HCOO and [Hnmp]HCOOO were obtained by geometrical optimization. Then the reaction mechanisms between [Hnmp]HCOOO and the three thiophene compounds were explored. The most likely transition states and intermediates were then investigated, and the energy change for each reaction step was calculated. According to the reaction mechanism, the oxidation of the thiophene compounds using peroxide [Hnmp]HCOOO had undergone processes of sulfoxide formation and sulfone formation. The results show that the ODS reaction rate of DBT is the most rapid, which is in accordance with the experimental results in reference; and the desulfurization efficiency of the H2O2/[Hnmp]HCOO system is higher than that of the traditional H2O2/HCOOH system.
中文标题：H2O2[Hnmp]HCOO氧化苯并噻吩类硫化物的量子化学研究
英文标题：Quantum Chemical Study on H2O2/[Hnmp]HCOO Ionic Liquid in the Oxidative Desulfurization of Sulfides
发表时间：2016-08-06
作者：
王寒露，周 臻，陈华锴
作者简介：
王寒露（1981-），女，博士，副教授，主要从事催化化学与计算化学研究。
关键词：离子液体,硫化物,密度泛函理论,氧化萃取脱硫,
Key words：ionic liquid,sulfides,DFT,oxidation extraction desulfurization,
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