NO在Ni_xAg_y(x+y=13)团簇表面吸附分解的第一性原理研究
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摘要
基于第一性原理计算方法,对Ni_xAg_y(x+y=13)团簇的几何结构进行优化后,研究了NO在此类团簇表面不同位置的吸附分解行为,讨论了团簇的束缚能、束缚能的二阶差分、能隙以及吸附前后键长、吸附能、NO分波态密度的变化情况.结果表明,团簇对称性随着Ni的占比变化而变化,稳定性随Ni占比增加而增强,束缚能的二阶差分随着Ni原子的增多呈现奇偶震荡性,NO@Ni_xAg_y(x+y=13)团簇表面吸附行为主要为化学吸附,吸附后N-O键长的变化在0.028?～0.092?之间.对团簇吸附NO的态密度分析发现,吸附后NO的2π*轨道失去电子,1π轨道得到电子,从而导致吸附能的变化.
Based on the first-principles calculation method, the geometrical structures of Ni_xAg_y(x+y=13) clusters were optimized. After changing the number of Ni atom in clusters, the surface adsorption behavior of NO molecules was studied. Before and after adsorption, the second order difference, the energy gap and the change of bond length were discussed. Calculated results showed that the cluster symmetry is changed with the change of Ni ratio, and the stability increases accompany with the increasing number of Ni atom. Obviously, a second order difference of the binding energy exhibits odd and even oscillations with the increasing number of Ni atom. Surface adsorptions of these clusters are mainly chemical adsorption. After adsorption, the change range of N-O length is between 0.028 ? and 0.091 ?. The PDOS of NO showed that after adsorption, the 2π* orbits of NO lose electrons and the 1π orbits get electrons, which leads to the change of adsorption energy. The different number of Ni atom in the clusters affect the 1π orbits getting electrons and eventually leading to different catalytic properties.
Based on the first-principles calculation method, the geometrical structures of Ni_xAg_y(x+y=13) clusters were optimized. After changing the number of Ni atom in clusters, the surface adsorption behavior of NO molecules was studied. Before and after adsorption, the second order difference, the energy gap and the change of bond length were discussed. Calculated results showed that the cluster symmetry is changed with the change of Ni ratio, and the stability increases accompany with the increasing number of Ni atom. Obviously, a second order difference of the binding energy exhibits odd and even oscillations with the increasing number of Ni atom. Surface adsorptions of these clusters are mainly chemical adsorption. After adsorption, the change range of N-O length is between 0.028 ? and 0.091 ?. The PDOS of NO showed that after adsorption, the 2π* orbits of NO lose electrons and the 1π orbits get electrons, which leads to the change of adsorption energy. The different number of Ni atom in the clusters affect the 1π orbits getting electrons and eventually leading to different catalytic properties.
引文
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[6] Liu T,Li Z,Ji Q,et al.Structural optimization of Fen-Ptm(5≤n+m≤24) alloy clusters based on an improved Basin-Hopping Monte Carlo algorithm[J].Acta Phys.Sin.,2017,66:51 (in Chinese) [刘暾东,李泽鹏,季清爽,等.基于改进Basin-Hopping Monte Carlo算法的Fen-Ptm(5≤n+m≤24)合金团簇结构优化[J].物理学报,2017,66:51]
[7] Mi H,Wei S,Duan X,et al.Catalytic reduction of N2O by CO over PtlAum- clusters:A first-principles study[J].Chinese Phys.B,2015,24:557.
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[9] Long J,Qiu Y,Wang S.A DFT study of 5d transition metal impurities encapsulated in the icosahedral and cuboctahedral Ag12 cages[J].Acta Phys.Sin.,2008,66:1771 (in Chinese) [龙娟,仇毅翔,王曙光.5d过渡金属原子中心镶嵌Ag团簇M@Ag12(M=Hf～Hg)Ih和Oh构型的密度泛函理论研究[J].化学学报,2008,66:1771]
[10] Reuse F A,Khanna S N,Bernel S.Electronic structure and magnetic behavior of Ni13 clusters[J].Phys.Rev.B,1995,52:11650.
[11] Sun H,Ren Y,Wang G.Equilibrium geometries of Nin (n = 2-20) clusters[J].J.At.Mol.Phys.(原子与分子物理学报),2001,18:387 (in Chinese)
[12] Cheng Z,Fu C,Bai J.First principles study of geometry structures and properties of ComAgn (m+n=13) clusters[J].J.At.Mol.Phys.(原子与分子物理学报),2015,32:993 (in Chinese)
[13] Zhang H,Watanabe T,Okumura M,et al.Catalytically highly active top gold atom on palladium nanocluster[J].Nat.Mater,2011,11:49.
[14] Mahara Y,Ishikawa H,Ohyama J,et al.Enhanced CO oxidation activity of Ni@Ag core–shell nanoparticles[J].Chem.Lett.,2014,43:910.
[15] Jiang X,Dong K,Wang H,et al.Liquid-phase hydrogenation of nitrobenzene over Ag-Ni bimetallic catalysts prepared by adsorption phase synthesis[J].Chin.J.Catal.,2010,31:1151 (in Chinese)
[16] Delley B.From molecules to solids with the DMol3 approach[J].J.Chem.Phys.,2000,113:7756.
[17] Hou M,Mei Q,Han B.Solvent effects on geometrical structures and electronic properties of metal Au,Ag,and Cu nanoparticles of different sizes[J].J.Colloid Interface Sci.,2015,449:488.
[18] Liu X,Wu Y,Li Z,et al.Energy gap of extended states in SiC-doped graphene nanoribbon:Ab initio calculations[J].Appl.Surf.Sci.,2017,400:1.
[19] Wang X,Wang X.Adsorption of small molecules on selected pure and Pd-doped gold Icosahedral clusters[J].J.Chongqing Univ.Technol.:Nat.Sci.,2014,28:147 (in Chinese) [王雪方,王新强.金及二元合金团簇吸附小分子的第一性原理研究[J].重庆理工大学学报,2014,28:147]
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