Keggin型磷钼酸负载金属单原子催化剂催化CO氧化的理论研究  

Theoretical Study on the Catalytic Oxidation of CO by Keggin Phosphomolybdate-Supported Metal Single Atom-Catalysts

作　　者：赵路菊 王凯洁 张立龙 陈丹丹 龙鲜桃 李小亚 虞程苹 李虎[1] 杨松[1] ZHAO Luju;WANG Kaijie;ZHANG Lilong;CHENG Dandan;LONG Xiantao;LI Xiaoya;YU Chengping;LI Hu;YANG Song(State-Local Joint Laboratory for Comprehensive Utilization of Biomass,Center for R&D of Fine Chemicals,Guizhou University,Guiyang 550025,China;School of Chemistry and Chemical Engineering,Guizhou University,Guiyang 550025,China)

机构地区：[1]贵州大学生物质资源综合利用国家地方联合工程实验室,精细化工研究开发中心,贵州贵阳550025 [2]贵州大学化学与化工学院,贵州贵阳550025

出　　处：《贵州大学学报（自然科学版）》2024年第6期34-40,共7页Journal of Guizhou University:Natural Sciences

基　　金：贵州大学SRT资助项目(贵大SRT字[2022]152号)。

摘　　要：随着工业化进程的加快,有害气体一氧化碳(CO)的排放量也在不断上升。为保护人类的健康,迫切需要实现CO的高效燃烧。运用密度泛函理论(density functional theory,DFT)详细分析了磷钼酸(PMA)载体上金属单原子催化剂(SACs)M_(1)/PMA(PMA=[PMo_(12)O_(40)]^(3-);M=Mn,Fe,Co,Ni,Ru,Rh,Pd,Re,Os,Ir,Pt)催化一氧化碳(CO)的反应机制,考察了分子几何构型、电子结构及金属与CO之间的相互作用。结果显示:吸附能的适中程度对催化效率至关重要,既能促进CO的有效吸附又能保证其顺利脱附。在各类SACs中,Pd_(1)/PMA因其适宜的吸附能和稳定的金属-氧相互作用而被认为是高效催化CO的理想选择,决速步的能垒仅为13.6 kcal/mol。这些发现不仅对CO的催化转化具有实际应用价值,也对未来的催化剂设计提供了重要指导。With the rapid development of industry,the emission of the toxic gas crab on monoxide(CO)is increasing,the complete combustion of CO for the sake of human health is necessary.In this study,we employed density functional theory to thoroughly investigate the catalytic mechanism of carbon monoxide(CO)on metal single-atom catalysts(SACs)supported by phosphomolybdic acid(PMA)M_(1)/PMA(PMA=[PMo_(12)O_(40)]^(3-);M=Mn,Fe,Co,Ni,Ru,Rh,Pd,Re,Os,Ir,and Pt),focusing on the molecular geometry,electronic structure,and the interaction between metal and CO.We discovered that a moderate adsorption energy was crucial for catalytic efficiency,facilitating effective CO adsorption and ensuring its smooth desorption.Among various SACs,Pd_(1)/PMA emerged as an ideal candidate for efficient CO catalysis due to its appropriate adsorption energy and stable metal-oxygen interaction,with the rate-determining step barrier being only 13.6 kcal/mol.These findings not only have practical implications for the catalytic transformation of CO but also provide significant guidance for the design of future catalysts.

关 键 词：磷钼酸 CO转化 金属单原子催化剂 密度泛函理论 

分 类 号：O643.3[理学—物理化学]