期刊
RSC ADVANCES
卷 3, 期 35, 页码 15225-15236出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3ra41284a
关键词
-
资金
- Key Project of the Ministry of Education of China [210189]
- Program for New Material Development & Application Innovative Research Team of Higher Education in Chongqing of China [201042]
- Chongqing Science & Technology Commission, China [CSTC2013JCYJA50028]
The mechanism of CO oxidation catalyzed by a 55-atom copper nanocluster was studied at the BVP86/DNP level with all-electron scalar relativity. Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms were studied in detail. Adsorption of O-2 on the copper cluster was prior to that of CO. The ER mechanism included three pathways, i.e. the O-2 dissociation, the O abstract from the O-2-pre-adsorbed Cu-55 cluster by the gaseous CO, and the insertion of CO into the O-O bond of the O-2-precovered Cu-55 cluster to form a carbonate-like intermediate to complete the CO oxidation. The LH mechanism was originated from the co-adsorption of CO and O-2 on the Cu-55 cluster and had three pathways to the final product. The reaction channels involving the O-2 dissociation, the O-abstraction, and the insertion of CO into the O-O bond vied with each other. The commonly accepted LH mechanism via the peroxo-like intermediate was unfeasible because of the unstable co-adsorption of CO and O-2 on the Cu-55 cluster. After incorporating the entropy effect, the CO-assisted O-2 dissociation pathway was the most feasible reaction channel above 250 K. The strong interaction of oxygen atom with the copper surface was in favour of the O-2 dissociation step, and was adverse to the reaction of the atomic oxygen toward CO to form CO2.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据