Co^(q)_(n)小团簇吸附活化原子氧的密度泛函研究  

A Density Functional Study on Adsorption of Activated Atomic Oxygen by C^(q)_(n) Small Clusters

作　　者：刘叶 袁佩[2] 朱裔荣[1] 陈文昊 颉雨佳[1] LIU Ye;YUAN Pei;ZHU Yirong;CHEN Wenhao;XIE Yujia(College of Materials and Advanced Manufacturing,Hunan University of Technology,Zhuzhou Hunan 412007,China;College of Chemical Engineering,Xiangtan University,Xiangtan Hunan 411105,China)

机构地区：[1]湖南工业大学材料与先进制造学院,湖南株洲412007 [2]湘潭大学化工学院,湖南湘潭411105

出　　处：《湖南工业大学学报》2022年第5期88-94,共7页Journal of Hunan University of Technology

基　　金：湖南省教育厅科研基金资助项目(17C0459,18B298,18C0527)。

摘　　要：利用基于密度泛函理论(DFT)的Dmol^(3)程序广义梯度近似PBE泛函,研究了Co^(q)_(n)(n=1~5;q=0,+,-)团簇和原子氧吸附在团簇上的几何结构、稳定性、电子性质和吸附反应行为。结果表明:Co^(q)_(n)团簇的几何结构保持不变,阳离子型团簇(Co^(+)_(n))的平均结合能远大于中性型(Co^(0)_(n))和阴离子型(Co^(-)_(n))团簇的平均结合能,这是因为团簇失去一个电子后可以显著增强该团簇的稳定性;原子氧在Co^(q)_(n)团簇顶位、桥位、空位的吸附稳定性、Co—O键长、原子氧的电荷转移都呈现出规律性变化,说明原子氧被活化;Co^(-)_(4) O B团簇的吸附能为-8.375 eV,轨道分析进一步表明其原子氧的2p轨道和钴的3d轨道杂化,相互作用为化学吸附。A research has been conducted on the geometric structure,stability,electronic properties and adsorption reaction behaviors of Co^(q)_(n)(n=1~5,q=0,+,-)clusters and atomic oxygen adsorbed on the clusters by using the generalized gradient approximation PBE functional of Dmol^(3) program based on density functional theory(DFT).The results indicate that the structure of Co^(q)_(n) clusters remains unchanged,while the average binding energy of the cationic cluster(Co^(+)_(n))is much higher than that of neutral clusters(Co^(0)_(n))and anionic clusters(Co^(-)_(n)),due to the fact that the loss of an electron can significantly enhance the stability of the cluster.The adsorption stability,the Co—O bond length and the charge transfer of atomic oxygen at the top site,bridge site and hole site of Co^(q)_(n) clusters show regular changes,which indicates that atomic oxygen is activated.When the adsorption energy of the Co-4O B cluster is-8.375 eV,the orbital analysis shows further that the 2p orbitals of atomic oxygen and the 3d orbitals of cobalt are hybridized,with an interaction a chemical adsorption.

关 键 词：Co^(q)_(n)团簇 Co^(q)_(n)O团簇 密度泛函理论 吸附 电子性质 

分 类 号：O562.4[理学—原子与分子物理]