DFT研究负载于ZrO_2(111)上Ni簇的CO甲烷化:微粒尺寸的影响（英文）
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摘要
采用量子化学密度泛函理论(DFT)研究了负载型催化剂Ni/ZrO_2(111)的CO甲烷化活性和选择性.结果表明:CO→CHO→CH_2O→CH_2→CH_3→CH_4是Ni_4-ZrO_2(111)面上CH_4形成的有利路径,CO→HCO→CH→CH_2→CH_3→CH_4是Ni_(13)-ZrO_2(111)面上CH_4形成的有利路径,这两种催化剂具有相似的CH_4生成活性,Ni_(13)-ZrO_2(111)比Ni_4-ZrO_2(111)具有明显高的CH_4选择性.Ni_4·ZrO_2(111)能较好地抑制积碳.
The density functional theory(DFT)method has been used to reveal the underlying mechanism of Ni cluster supported on ZrO_2(111)as well as the activity and selectivity of CO methanation.CO→HCO→CH_2O→CH_2→CH_3→CH_4is mainly responsible for CH_4 formation on Ni_4-ZrO_2(111),while CH_4 is mainly formed via the path of CO→ HCO→CH→CH_2 →CH_3 →CH_4 on Ni_(13)-ZrO_2(111).Ni_4-ZrO_2(111)and Ni_(13)-ZrO_2(111)exhibit similar activity for CH_4 formation with the free energy barrier of 2.38 eV and 2.26 eV,respectivley.In addition,Ni_(13)-ZrO_2(111)displays a remarkable high selectivity to CH_4 comparing with Ni_4-ZrO_2(111).Moreover,Ni_4-ZrO_2(111)exhibits high resistance to carbons,while Ni_(13)-ZrO_2(111)surface is much sensitively to form deposition carbon.
The density functional theory(DFT)method has been used to reveal the underlying mechanism of Ni cluster supported on ZrO_2(111)as well as the activity and selectivity of CO methanation.CO→HCO→CH_2O→CH_2→CH_3→CH_4is mainly responsible for CH_4 formation on Ni_4-ZrO_2(111),while CH_4 is mainly formed via the path of CO→ HCO→CH→CH_2 →CH_3 →CH_4 on Ni_(13)-ZrO_2(111).Ni_4-ZrO_2(111)and Ni_(13)-ZrO_2(111)exhibit similar activity for CH_4 formation with the free energy barrier of 2.38 eV and 2.26 eV,respectivley.In addition,Ni_(13)-ZrO_2(111)displays a remarkable high selectivity to CH_4 comparing with Ni_4-ZrO_2(111).Moreover,Ni_4-ZrO_2(111)exhibits high resistance to carbons,while Ni_(13)-ZrO_2(111)surface is much sensitively to form deposition carbon.
引文
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[2]MA Shengli,TAN Yisheng,HAN Yizhuo.Water-gas Shift Coupling with Methanation over MOx Modified Nanorod-NiO/γ-Al2O3 Catalysts[J].Journal of Industrial and Engineering Chemistry,2011,17(4):723-726.
[3]GUO Cuili,WU Yuanyuan,QIN Hongyun,et al.CO Methanation over ZrO2/Al2O3Supported Ni Catalysts:A Comprehensive Study[J].Fuel Processing Technology,2014,124:61-69.
[4]ZHANG Junfeng,BAI Yunxing,ZHANG Qingde,et al.Low-temperature Methanation of Syngas in Slurry Phase over Zrdoped Ni/γ-Al2O3Catalysts Prepared Using Different Methods[J].Fuel,2014,132:211-218.
[5]ZENG Yan,MA Hongfang,ZHANG Haitao,et al.Highly Efficient NiAl2O4-free Ni/γ-Al2O3Catalysts Prepared by Solution Combustion Method for CO Methanation[J].Fuel,2014,137:155-163.
[6]LU Huailiang,YANG Xuzhuang,GAO Guanjun,et al.Mesoporous Zirconia-modified Clays Supported Nickel Catalysts for COand CO2 Methanation[J].International Journal of Hydrogen Energy,2014,39(33):18894-18907.
[7]MENG Fanhui,LI Zhong,JI Fangkui,et al.Effect of ZrO2on Catalyst Structure and Catalytic Methanation Performance over Ni-based Catalyst in Slurry-bed Reactor[J].International Journal of Hydrogen Energy,2015,40(29):8833-8843.
[8]RAZZAQ R,ZHU Hongwei,JIANG Li,et al.Catalytic Methanation of CO and CO2in Coke Oven Gas over Ni-Co/ZrO2-CeO2[J].Industrial&Engineering Chemistry Research,2013,52(6):2247-2256.
[9]XAVIER K O,SREEKALA R,RASHID K K A,et al.Doping Effects of Cerium Oxide on Ni/Al2O3 Catalysts for Methanation[J].Catalysis Today,1999,49(1):17-21.
[10]RAHMANI Soudabeh,REZAEI Mehran,MESHKANI Fereshteh.Preparation of Promoted Nickel Catalysts Supported on Mesoporous Nanocrystalline Gamma Alumina for Carbon Dioxide Methanation Reaction[J].Journal of Industrial and Engineering Chemistry,2014,20(6):4176-4182.
[11]LIU Jiao,YU Jian,SU Fabing,et al.Intercorrelation of Structure and Performance of Ni-Mg/Al2O3Catalysts Prepared with Different Methods for Syngas Methanation[J].Catalysisence&Technology,2014,4(2):472-481.
[12]TRUEBA Monica,TRASATTI Stefano P.γ-Alumina as a Support for Catalysts:A Review of Fundamental Aspects[J].Cheminform,2005,36(44):3393-3403.
[13]BARRIENTOS J,LUALDI M,SUREZ PARS R,et al.CO Methanation over TiO2-supported Nickel Catalysts:A Carbon Formation Study[J].Applied Catalysis A:General,2015,502(29):276-286.
[14]ZKARA-AYDINOGLU Seyma,ZENSOY Emrah,ERHAN AKSOYLU A.The Effect of Impregnation Strategy on Methane Dry Reforming Activity of Ce Promoted Pt/ZrO2[J].International Journal of Hydrogen Energy,2009,34(24):9711-9722.
[15]IRIONDO A,CAMBRA J F,GEMEZ M B,et al.Effect of ZrO2 Addition on Ni/Al2O3 Catalyst to Produce H2from Glycerol[J].International Journal of Hydrogen Energy,2012,37(8):7084-7093.
[16]HUANG Yanhui,WANG Jijie,LIU Zhiming,et al.Highly Efficient Ni-ZrO2 Catalyst Doped with Yb2O3 for COMethanation of CO and CO2[J].Applied Catalysis A:General,2013,466(8):300-306.
[17]TAKENAKA SAKAE,SHIMIZU TORU,OTSUKA KIYOSHI.Complete Removal of Carbon Monoxide in Hydrogen-rich Gas Stream through Methanation over Supported Metal Catalysts[J].International Journal of Hydrogen Energy,2004,29(10):1065-1073.
[18]GAO Jiajian,JIA Chunmiao,ZHANG Meiju,et al.Effect of Nickel Nanoparticle Size in Ni/α-Al2O3on CO Methanation Reaction for the Production of Synthetic Natural Gas[J].Catalysis Science&Technology,2013,3(8):2009-2015.
[19]WANG Yang,ZHU Mingyuan,KANG Lihua,et al.Neutral Aun(n=3-10)Clusters Catalyze Acetylene Hydrochlorination:A Density Functional Theory Study[J].RSC Advances,2014,4(72):38466-38473.
[20]KRESSE G,FURTHMLLER J.Efficient Iterative Schemes for Ab Initio Total-energy Calculations Using A Plane-wave Basis Set[J].Physical Review B:Condensed Matter,1996,54(16):11169-11186.
[21]KRESSE G,HAFNER J.Ab Initio Molecular Dynamics for Liquid Metals[J].Physical Review B:Condensed Matter,1993,47(1):558-561.
[22]KRESSE G,JOUBERT D.From Ultrasoft Pseudopotentials to the Projector Augmented-wave Method[J].Physical Review B:Condensed Matter,1999,59(3):1758-1775.
[23]METHFESSEL M,PAXTON A T.High-precision Sampling for Brillouin-zone Integration in Metals[J].Physical Review B:Condensed Matter,1989,40(6):3616-3621.
[24]MONKHORST H J,PACK J D.Special Points for Brillouin-zone Integrations[J].Physical Review B:Condensed Matter,1976,16(4):5188-5192.
[25]SHEPPARD D,XIAO P,CHEMELEWSKI W,et al.A Generalized Solid-state Nudged Elastic Band Method[J].Journal of Chemical Physics,2012,136(7):074103-1-8.
[26]SHEPPARD D,TERRELL R,HENKELMANA G.Optimization Methods for Finding Minimum Energy Paths[J].Journal of Chemical Physics,2008,128(13):134106-134110.
[27]OLSEN R A,KROES G J,HENKELMAN G,et al.Comparison of Methods for Finding Saddle Points Without Knowledge of the Final States[J].Journal of Chemical Physics,2004,121(20):9776-9792.
[28]KAPUR NEETI,HYUN JANGSUK,SHAN BIN,et al.Ab Initio Study of CO Hydrogenation to Oxygenates on Reduced Rh Terraces and Stepped Surfaces[J].Journal of Chemical Physics,2010,114(22):10171-10182.
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[30]ZHI Cuimei,ZHANG Riguang,WANG Baojun.Comparative Studies About CO Methanation over Ni(211)and Zr-modified Ni(211)Surfaces:Qualitative Insight into the Effect of Surface Structure and Composition[J].Molecular Catalysis,2017,438:1-14.
[31]ANDERSSON M P,ABILD-PEDERSEN F,REMEDIAKIS I N,et al.Structure Sensitivity of the Methanation Reaction:H2-induced CO Dissociation on Nickel Surfaces[J].Journal of Catalysis,2008,255(1):6-19.