在Pd1-Cu(111) 和Pd1-Ag(111) 催化剂上对CO2化成甲醇的微动力学研究:DFT分析
Abdulrauf Onimisi Ibrahim1,2,3, Wan Mohd Ashri Wan Daud1,2, Muhamad Fazly Abdul Patah1,2
1Department of Chemical Engineering, University of Malaya, Kuala Lumpur, Malaysia. ashri@um.edu.my.
本研究使用DFT来研究Pd单原子合金催化剂的二氧化碳转化为甲醇. 研究结果显示,Pd增强了CO2的激活,通过Pd1-Ag上的特定反应途径有利于甲醇的产生.
科学领域:
- 催化剂是一种催化剂.
- 材料科学 材料科学 材料科学
- 计算化学计算化学
背景情况:
- 二氧化碳 (CO2) 热化学转化为甲醇 (CH3OH) 是至关重要的,但受到恶劣条件下的逆水气反应的阻碍.
- 催化剂不稳定性和高能源成本需要理论方法来优化甲醇合成.
- 过渡金属,特别是 (Pd),作为选择性二氧化碳化的单原子催化剂具有前景.
研究的目的:
- 在Pd1-Cu(111) 和Pd1-Ag(111) 单原子合金 (SAA) 催化剂上理论上探索CO2到CH3OH的转化途径.
- 阐明单个Pd原子在增强CO2激活和甲醇选择性的作用.
- 确定在这些SAA催化剂上产生甲醇的最有利反应机制.
主要方法:
- 用密度函数理论 (DFT) 的计算来建模催化系统.
- 微动力反应建模被用来绘制复杂的二氧化碳化路径.
- 吸附能量,过渡状态和热力学/动力学概况被系统地分析.
主要成果:
- 单个Pd原子在Pd1-Cu(111) 和Pd1-Ag(111) 表面显著增强了CO2激活.
- 研究了三种不同的反应途径 (COOH*,HCOO*,CO解离),具有不同的能量场景.
- 在Pd1-Ag(111) 上,确定HCOO*路径是最受欢迎的路径,涉及连续的中间体,导致CH3OH形成,激活能量较低.
结论:
- 具有Pd的单原子合金对二氧化碳转化为甲醇有效,减轻了与传统催化剂相关的问题.
- 单个Pd原子在SAA表面的精确几何排列允许控制反应路径和提高选择性.
- DFT和微动力学建模为了解和设计用于可持续化学生产的先进催化材料提供了强大的框架.
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