Density Functional Theory for the Investigation of Catalytic Activity of X@Cu12 (X =Cu, Ni, Co, or Fe) for N2O Decomposition

摘要

We have investigated the reaction mechanism for N2 O decomposition on Cu13 via density functional theory. It is found that N2 O decomposition on the cluster is more prone to be along the Eley-Rideal(ER) pathway in comparison with the Langmuir-Hinshelwood(LH) channel. There exists structural relaxation for Cu13 cluster in the reaction, which may influence the catalytic activity of cluster for the subsequent N2 O decomposition. The core atom in the Cu13 cluster is substituted with the Fe, Co, or Ni to enhance structural stability and prevent from the obvious configuration relaxation in the reaction. Note that these bimetallic clusters are of icosahedra as the Cu13. They have activities for N2 O dissociation along ER pathway and the heteroatom in the cluster can prevent configuration from relaxation. Finally, the Ni@Cu12 cluster can be as a superior catalyst in a complete catalytic cycle via comparison in this study.