Mechanism Elucidation of Dioxins Decomposition on an oxide catalysis using Ab-initio molecular orbiral calculation

本研究利用从头算分子轨道计算方法，对二恶英在金属氧化物催化剂上的分解反应机理进行了探讨。本文首先阐述了二恶英氧化分解的反应过程。二恶英分解的主要途径有以下三种：（1）氯原子解离。（2）桥氧原子的解离。（3）苯环断裂。在本研究中，我们的注意力集中在桥氧化物原子的解离。具体而言，我们选择了非氯化二苯并对二恶英（NCDD）作为目标分子。然后，我们认为，一些分解途径将取决于不同的氧吸附位置的NCDD。我们揭示了二恶英与催化剂表面的相互作用。以C16-苯为目标分子，Cu 6为催化剂模型。在该反应中，我们将注意力集中在催化剂表面的分子吸附反应。结果表明，二恶英与催化剂表面的反应机理存在一定的相关性，反应机理对团簇大小的影响也很明显。

In this study, we have pursued the reaction mechanism elucidation of dioxin decomposition reaction on oxide-metal-catalyst using ab-initio molecular orbital calculation. At first, we have elucidated the reaction process of dioxin oxidation decomposition. Major pathways of dioxin decomposition are known as the following three pathways : (1)dissociation of chlorine atom. (2)dissociation of bridged oxide atom. (3)splitting of benzene-ring. In this research, we have focused our attention on the dissociation of bridged oxide atom. Specifically, we have chosen non-chlorinated-dibenzo-para-dioxin (NCDD) as a target molecular. Then, we have considered that some decomposition pathways would depend on difference in oxygen adsorption position on NCDD. We have revealed the interaction of dioxin with the surface of a catalyst. We have C16-benze as a target molecular and Cu6 as catalyst model. In this reaction, we have focused our attention on molecular adsorbing reaction on catalyst surface. As the result, we have acquired knowledge of correlation with the reaction mechanism on dioxin and the catalyst surface, and we have clarified the cluster size depend on reaction mechanism.