NO在Ir(111)表面吸附与解离的第一性原理研究
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摘要
本文系统研究了NO在Ir(111)表面的吸附,解离,以及可能的N_2生成机理.结果表明,顶位吸附的NO,其解离能垒较高(3.17 eV),不会发生解离,而三重Hcp和Fcc空位吸附的NO发生解离,能垒分别为1.23和1.28 eV.N_2是唯一的生成物,不会有副产物N_2O的产生.其最可能的反应路径为N和NO经过N_2O中间体而生成N_2,而不是直接N提取和N-N聚合产生N_2的机理.
The mechanism of NO adsorption and dissociation on Ir( 111) surface and the possible mechanism of N_2 formation were studied. The results show that the NO adsorbed on Hcp and Fcc sites dissociate,while those adsorbed on top site do not dissociate due to the very high dissociation barrier. Three dissociation pathways for the N_2 formation were located,and the results show that N + NO → N_2O → N_2+ O isthe predominant N_2 formation pathway,while the N + N → N_2 pathway is also involved but less competitive.
The mechanism of NO adsorption and dissociation on Ir( 111) surface and the possible mechanism of N_2 formation were studied. The results show that the NO adsorbed on Hcp and Fcc sites dissociate,while those adsorbed on top site do not dissociate due to the very high dissociation barrier. Three dissociation pathways for the N_2 formation were located,and the results show that N + NO → N_2O → N_2+ O isthe predominant N_2 formation pathway,while the N + N → N_2 pathway is also involved but less competitive.
引文
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[2]King D A.Climate Change Science:Adapt,Mitigate,or Ignore[J].Science,2004,303:176.
[3]Shelef,Graham GW.Why rhodium in automotive three-way Catalysts[J].Catal.Rev.Sci.Eng.,1994,36:433.
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[6]Fujitani T,Nakamura I,Takahashi A,et al.Kinetics and mechanism of NO reduction with CO on Ir surfaces[J].J.Catal.,2008,253:139.
[7]Gardner P,Martin R,Nalerinski R,et al.Adsorption of nitric oxide on Ir{100}:influence of substrate reconstruction[J].J.Chem.Soc.Faraday Trans.,1995,91:3575.
[8]Khatua S,Held G,King D A.Model car-exhaust catalyst studied by TPD and TP-RAIRS:Surface reactions of NO on clean and O-covered Ir{100}[J].Surf.Sci.,2005,586:1.
[9]Khatua S,Liu Z P,King D A.NO restructuring of surface Ir and bond formation to preadsorbed O on Ir{100}at 95 K[J].Surf.Sci.,2005,584:214.
[10]Arnolds H,King D A,Lane I M.Inducing non-adiabatic effects through coadsorption:CO+NO on iridium[J].Chem.Phys.,2008,350:94.
[11]Nakamura,Suzuki K,Takahashi A,et al.Reaction properties of NO and CO over an Ir(211)surface,[J]J.Vac.Sci.Technol.A,2007,25:1143.
[12]Fujitani T,Nakamura I,Kobayashi Y,et al.Adsorption and Reactions of NO on Clean and CO-Precovered Ir(111)[J].J.Phys.Chem.B,2005,109:17603.
[13]Chen W H,Shen Q T,Bartynski R A,et al.Reduction of NO by CO on unsupported Ir:bridging the materials gap[J].Chem.Phys.Chem.,2010,11:2515.
[14]Nakamura,Fujitani T.Adsorption behavior and reaction properties of NO and CO on Ir(111)and Rh(111)[J].Catal Surv Asia,2009,13:22.
[15]Hamersb R J,Houston P L,Merrill R P.Gas-surface interactions with vibrationally excited molecules[J].J.Chem.Phys.,1988,88:6548.
[16]Davis J E,Karseboom S G,Nolan P D,et al.Kinetics and dynamics of the initial adsorption of nitric oxide on Ir(111)[J].J.Chem.Phys.,1996,105:8362.
[17]Zeng Z H,Juarez L F,Silvab D,et al.Theory of nitride oxide adsorption on transition metal(111)surfaces:a first-principles investigation[J].Phys.Chem.Chem.Phys.,2010,12:2459.
[18]Liu Z P,Jenkins S J,King D A.Step-enhanced selectivity of NO reduction on platinum-group metals[J].J.Am.Chem.Soc.,2003,125:14660.
[19]Krekelberg W P,Greeley J,Mavrikakis M.Atomic and molecular adsorption on Ir(111)[J].J.Phys.Chem.B,2004,108:987.
[20]Wang M M,Huang X Y,Li J,et al.Adsorption of atoms,molecules and radicals on Ni(100)surface:A first-principles study[J].J.At.Mol.Phys.,2016,33:161(in Chinese)[王萌萌,黄晓玉,李婧,等.原子分子在Ni(100)表面吸附的第一性原理研究[J].原子与分子物理学报,2016,33:161]
[21]Zhang Q J,Gao Z Z,Yuan Y,et al.First principles study of the influence of charged state on Pd13cluster catalytic activity for NO decomposition.[J].J.At.Mol.Phys.,2016,33:438[张秋杰,高占忠,原玉,等.第一性原理研究荷电状态对Pd13团簇催化分解NO性能的影响[J].原子与分子物理学报,2016,33:438]
[22]Kresse G,Hafner J.Ab initio molecular dynamics for liquid metals[J].Phys.Rev.B,1993,47:558
[23]Blo P E,Projector augmented-wave method[J].Phys.Rev.B.1994,50:17953.
[24]Kresse G,Joubert D,Form ultrasoft pseudopotentials to the projector augmented-wave method[J].Phys.Rev.B,1999,59:1758
[25]He C Z,Wang H,Huai L Y,et al.Mechanism of ammonia decomposition and oxidation on Ir(100):A first-principles study[J].J.Phys.Chem.C,2012,116:24035
[26]Tang Y N,Chen W G,Li C G,et al.Theoretical study on catalytic property of metallic atom decorated graphene sheets[J].J.At.Mol.Phys.,2016,33:711[唐亚楠,陈卫光,李成刚,等.金属原子修饰石墨烯体系催化性能的理论研究[J].原子与分子物理学报,2016,33:711]
[27]Zheng Y F,Dong L Y,Cao R Y,et al.5d transition metals adsorbed boron nitride nanotubes-a first principles calculation[J].J.At.Mol.Phys.,2015,32:408[郑宇斐,董丽元,曹茹月,等.5d过渡金属原子吸附氮化硼纳米管的第一性原理计算[J].原子与分子物理学报,2015,32:408]