Th_(2)^(+/0/-)不同电荷态对N_(2)O氧化CO反应的影响  

Oxidation reactions of CO by N_(2)O on Th_(2)^(+/0/-)clusters:The effect of charge states of ThO_(2)

作　　者：夏婵娟 石锦豪 张惠孜 李大武 岳光辉[1] XIA Chan-Juan;SHI Jin-Hao;ZHANG Hui-Zi;LI Da-Wu;YUE Guang-Hui(Department of Criminal Science and Technology,Hunan Police Academy,Changsha 410138,China;The Key Laboratory of Impression Evidence Examination and Identification Technology,Ministry of Public Security,Shenyang 110033,China;College of Forensic Science and Technology,Criminal Investigation Police University of China,Shenyang 110035,China)

机构地区：[1]湖南警察学院刑事科学技术系,长沙410138 [2]痕迹检验鉴定技术公安部重点实验室,沈阳110033 [3]中国刑事警察学院刑事科学技术学院,沈阳110035

出　　处：《原子与分子物理学报》2023年第1期53-66,共14页Journal of Atomic and Molecular Physics

基　　金：国家自然科学基金(21301030);痕迹检验鉴定技术公安部重点实验室开放课题(2018HJKF12);湖南省大学生创新创业训练计划项目;湖南警察学院道路交通安全执法关键技术科研创新团队。

摘　　要：本文采用密度泛函理论,对Th_(2)^(+/0/-)团簇参与CO与N_(2)O间氧化还原反应(CO+N_(2)O→CO_(2)+N_(2))的机理展开研究,探讨钍氧团簇所带的电荷对该反应的影响.研究表明:Th_(2)^(+/0/-)在反应中主要起传输氧原子的作用,其中Th_(2)^(O+)与CO的反应以及ThO+/0/-与N_(2)O的反应都为热力学上的放热反应,而ThO_(2)^(0/-)与CO的反应为热力学上的吸热反应.随着电荷态的改变,Th_(2)^(+/0/-)与CO反应的总能垒(E_(b))与总驱动力(-ΔG)有较大差异.因此,通过改变ThO_(2)的电荷态能调节其对CO/N_(2)O反应的催化活性,综合考虑,Th_(2)^(O+)对于CO/N_(2)O氧化还原反应的潜在催化活性最高.Density functional theory(DFT)calculations at the B3LYP level are performed to investigate the redox reactions between CO and N_(2)O in which Th_(2)^(+/0/-)clusters participate.The reaction mechanisms are illustrated and the impacts of the charge states of Th_(2)^(+/0/-)on the above reactions are evaluated as well.Our results show that Th_(2)^(+/0/-)play the role of transporting O atom in the CO/N_(2)O redox reaction.The reaction of Th_(2)^(O+)with CO is exothermic,while those of ThO-/02 with CO are endothermic.As for the reactions of ThO+/0/-with N_(2)O,they are all exothermic.With the change of the charge state,the energy barriers(E_(b))and the driving forces(-ΔG)of the overall reactions show big differences for Th_(2)^(O+),ThO_(2)and ThO-2 reacting with CO,respectively.Therefore,by changing the charge state of ThO_(2),its redox ability can be regulated.In summary,the positively charged Th_(2)^(O+)cluster shows the highest catalytic activity in the above CO/N_(2)O redox reaction.

关 键 词：钍氧簇 密度泛函理论 电子结构 催化氧化反应 电荷 

分 类 号：O641[理学—物理化学]