羟基化氧化锌催化甲醇裂解反应机理的理论研究

Theoretical Study of the Reaction Mechanism of Hydroxyl ZnO Catalyzing Methanol Decomposition

采用密度泛函理论的B3LYP方法在两种基组水平上研究了羟基化氧化锌催化裂解甲醇反应机理,优化了反应过程中各反应物、中间体、过渡态和产物几何构型,并且应用了自然轨道理论(NBO)和分子中的原子理论(AIM)分析了这些物质的成键特征和轨道间的相互作用.研究中分别采用了羟基化一个ZnO和羟基化两个ZnO作为催化剂的两种简化模型.结果表明两种不同基组研究所得的反应历程及相应能量变化趋势一致;羟基化两个ZnO催化剂活化裂解甲醇反应更容易发生.

The reaction mechanism of ZnO catalyzing methanol decomposition has been investigated by B3LYP method of density function theory at two different levels. The geometries of reactants, intermediates, transistion states and products have been calculated. In addition, nature bond orbital （NBO） and atoms in molecules （AIM） theories have been used to discuss bond natures and orbital interactions. The two simplified models of single ZnO with hydroxyl group and double ZnO with hydroxyl group have been used in the research respectively. The results of two different levels indicated that the reaction mechanism and the change trend of correspondence energy were consistent, and the reaction which was catalyzed by double ZnO with hydroxyl group was easier to occur.