活性炭酚羟基和羧基对二苯并噻吩吸附作用的分子模拟研究  

A molecular simulation study of phenolic hydroxyl and carboxyl on activated carbon surface on its adsorption behavior for dibenzothiophene

作　　者：高宇[1] 杜旭东[1] 卞杨燕[1] 崔群[1] 王海燕[1] 姚虎卿[1] 

机构地区：[1]南京工业大学化学化工学院,江苏南京210009

出　　处：《计算机与应用化学》2011年第10期1335-1338,共4页Computers and Applied Chemistry

摘　　要：采用密度泛函理论计算酚羟基、羧基和二苯并噻吩的结构以及酚羟基和羧基吸附二苯并噻吩后的结构;用"分子内原子理论"计算酚羟基和羧基吸附二苯并噻吩后体系的电荷密度及其拉普拉斯值;用"自然键轨道理论"计算酚羟基与二苯并噻吩之间的电荷转移。结果表明:酚羟基与二苯并噻吩之间形成了O-H…π芳香氢键,其结合能为7.97 kJ·mol^(-1);成键路径为从酚羟基的H_(34)开始,指向二苯并噻吩的C_1=C_2;酚羟基与二苯并噻吩形成芳香氢键的原因是其反键轨道σ_(O33-H34)~*与二苯并噻吩的π体系π_(C1=C2)存在交互作用;约有5.29×10^(-22) C的电荷从二苯并噻吩的C_1=C_2转移至酚羟基的σ_(O33-H34)~*;羧基未与二苯并噻吩形成氢键。增加活性炭表面酚羟基含量,将有利于提高活性炭对DBT的吸附容量。The structures of phenolic hydroxyl, carboxyl, dibenzothiophene as well as their complexes on activated carbon surface were investigated using density functional theory （DFT）. The theory of Atoms in Molecules was used to calculate the theoretical charge density and its Laplacian value. Intermolecular charge transfer between dibenzothiophene and phenolic hydroxyl was analyzed by performing natural bond orbital calculations. Based on a theoretical study of the adsorption complex, the authors have established the existence of π…H hydrogen bond between dibenzothiophene and phenolic hydroxyl, with a 7.97 kJ.mol^-1 interaction energy. This bond path goes from the H34 to the C1=C2 bond. Charge transfer （5.29×10^-22 C） from π electron systems （πc1=c2） of dibenzothiophene to the anti-bond orbital （σ o33-H34） might be the reason for the formation of this hydrogen bond. No hydrogen bond between dibenzothiophene and carboxyl can be observed. The increase of phenolic hydroxyl on activated carbon surface may improve adsorptive capacity of activated carbon for dibenzothiophene.

关 键 词：密度泛函理论 二苯并噻吩 酚羟基 羧基 氢键 

分 类 号：TE624[石油与天然气工程—油气加工工程] O622.7[理学—有机化学]