摘要
采用杂化泛函B3LYP对溶液环境Pt催化N2H4分解过程中N—N断键、N—H断键过渡态结构进行模拟计算和IRC验证,并对反应物、产物等结构进行了几何优化。结果表明:得到了中性、酸性溶液条件下N—N断键以及N—H断键过渡态结构及其热力学数据;酸性条件有利于N—N断键,随着溶液酸性增强,N—N断键越容易;N原子上的H原子会被H2O吸引而偏转,导致酸性条件N—N断键过渡态结构发生变化;酸性溶液中N—H断键受到H+抑制影响较大,能垒与中性溶液相比有大幅度升高,且会发生N—H断键逆反应。
Hybrid functional B3LYP was used to simulate and IRC verify the transition state structures of N—N and N—H bond breaking in decomposition of N2H4 catalyzed by Pt in solution environment.The structures of reactants and products were geometrically optimized.The results show that:The thermodynamic data of N—N and N—H bond breaking transition states in neutral and acidic solution were obtained.Acidic conditions were favorable for N—N bond breaking,and the more acidic the solution was,the easier it was for N—N bond breaking.H atom on N atom will be attracted by H2O then deflected,leading to the change of the transition state structure of N—N bond breaking under acidic conditions.The N—H bond breaking in acidic solution is greatly affected by H+inhibition.The energy barrier is greatly increased compared with neutral solution,and the reverse reaction of N—H bond breaking will occur.
作者
唐菲菲
郝帅
张晓腾
石伟群
夏良树
TANG Feifei;HAO Shuai;ZHANG Xiaoteng;SHI Weiqun;XIA Liangshu(School of Nuclear Science and Technology,University of South China,Hengyang of Hunan Prov.421001,China;Laboratory of Nuclear Energy Chemistry,Institute ofHigh Energy Physics,Chinese Academy of Sciences,Beijing 100049,China)
出处
《核科学与工程》
CAS
CSCD
北大核心
2020年第2期333-340,共8页
Nuclear Science and Engineering
基金
国家自然科学基金资助项目(11575078)
湖南省研究生科研创新项目重点资助项目(CX20190713)。
关键词
肼
铂
过渡态
密度泛函理论
催化
Hydrazine
Platinum
Transient state
Density Functional Theory
Catalyst
作者简介
唐菲菲(1992-),女,四川乐山人,硕士研究生,现从事核燃料循环及材料方面研究;通信作者:夏良树:xls1966@hotmail.com。
