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

使用从头算分子轨道计算阐明氧化物催化二恶英分解的机理

• 批准号: 14550729
• 负责人: FUWA Akio
• 金额: $ 2.18万
• 依托单位: Waseda University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550729/
• 关键词: Ab-initio calculation; Dioxin; Decomposition; Reaction Mechanism; dioxins; catalyst; ab initio MO

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.

在这项研究中，我们利用从头计算分子轨道计算来阐明氧化物金属催化剂上二恶英分解反应的反应机理。首先阐明了二恶英氧化分解的反应过程。二恶英分解的主要途径已知为以下三种途径： (1)氯原子解离。 (2)桥接氧化物原子的解离。 (3)苯环裂解。在这项研究中，我们将注意力集中在桥接氧化物原子的解离上。具体来说，我们选择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取决于氧在 NCDD 上吸附位置的差异。我们揭示了二恶英与催化剂表面的相互作用。我们以 C16-苯作为目标分子，以 Cu6 作为催化剂模型。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，我们获得了二恶英和催化剂表面上的反应机理的相关性知识，并且我们澄清了取决于反应机理的簇尺寸。

项目成果

T.Araki, M.Hirota, A.Fuwa: Yazawa International Symposium METALLURGICAL AND MATERIALS PROCESSING. 1069-1077 (2003)

T.Araki、M.Hirota、A.Fuwa：矢泽国际冶金与材料加工研讨会。