Elucidation and Design of NO Reduction Reaction Process by First-Principles Multiscale Simulation

通过第一性原理多尺度模拟阐明和设计 NO 还原反应过程

• 批准号: 21J10648
• 负责人: PHAM THANH NGOC
• 金额: $ 0.96万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2021
• 资助国家: 日本
• 起止时间: 2021-04-28 至 2023-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-21J10648/
• 关键词: three-way catalyst; NO reduction reaction

We studied the co-adsorption of NO-H2O on Cu(111) using the van der Waals density functional theory method. We first studied the adsorption of NO and H2O clusters on Cu(111). The energetics, adsorption geometries, and vibrational properties of several NO-H2O complexes are estimated, and the relative stabilities of those complexes are compared with respective NO and H2O clusters on Cu(111). We find that the mixed complexes between NO and H2O on Cu(111) are more stable than the separated clusters of NO and water, which arises from the hydrogen bonding between NO and H2O and NO - NO interaction. Electronic structure analysis indicates that attractive NO-H2O interaction arises from the hydrogen bonding with the enhancements of back-donation to valence orbitals of NO, while the NO - NO interaction arises from the hybridization among valance orbitals. The vibrational analysis also confirms the formation of the mixed NO-H2O complexes and N-O stretching modes are red-shifted due to hydrogen bonding with water. Our result provides an insightful interpretation of experimental observation.We also have studied the metal-support interaction (MSI) of the platinum metal group (PGM) supported on some metal oxide materials under three-way catalyst (TWC) operating conditions using machine-learning enhanced global optimization and thermodynamics.

用范德华密度泛函理论方法研究了NO-H2O在铜(111)面上的共吸附。我们首先研究了NO和H2O团簇在铜(111)面上的吸附。估算了几种NO-H2O络合物的能级、吸附几何构型和振动性质，并与各自的NO和H2O团簇在铜(111)面上的相对稳定性进行了比较。结果表明，由于NO与H2O之间的氢键作用和NO-NO相互作用，NO与H2O在Cu(111)面上形成的混合络合物比NO与水分离的团簇更稳定。电子结构分析表明，具有吸引力的NO-H2O相互作用是由于NO对价轨道的回馈作用增强而形成的氢键作用，而NO-NO相互作用则是价轨道间的杂化作用。振动分析还证实了混合NO-H2O络合物的形成，N-O伸缩模式由于与水的氢键而红移。我们的结果为实验观察提供了一个有洞察力的解释。我们还利用机器学习增强的全局优化和热力学方法研究了一些金属氧化物材料负载的铂金属基团(PGM)在三效催化剂(TWC)操作条件下的金属-载体相互作用。