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学科主题: 物理化学
题名: Catalytic properties of extraframework iron-containing species in ZSM-5 for N2O decomposition
作者: Li, Guanna1, 2;  Pidko, Evgeny A.1;  Filot, Ivo A. W.1;  van Santen, Rutger A.1;  Li, Can2;  Hensen, Emie J. M.1
通讯作者: 李灿 ;  Emiel J.M. Hensen
关键词: Fe/ZSM-5 ;  DFT calculations ;  Zeolite ;  Reaction mechanism ;  Binuclear complexes ;  N2O decomposition ;  Microkinetic modeling
刊名: JOURNAL OF CATALYSIS
发表日期: 2013-12-01
DOI: 10.1016/j.jcat.2013.08.010
卷: 308, 页:386-397
收录类别: SCI
合作性质: 
文章类型: Article
部门归属: 5
项目归属: 503
产权排名: 待补充
WOS标题词: Science & Technology ;  Physical Sciences ;  Technology
类目[WOS]: Chemistry, Physical ;  Engineering, Chemical
资助者: 2,1
研究领域[WOS]: Chemistry ;  Engineering
英文摘要: The reactivity of mononuclear and binuclear iron-containing complexes in ZSM-5 zeolite for catalytic N2O decomposition has been investigated by periodic DFT calculations and microkinetic modeling. On mononuclear sites, the activation of a first N2O molecule is favorable. The rate of catalytic N2O decomposition over Fe2+ and [(FeO)-O-III](+) sites is very low because of the very high barriers (>180 kJ/mol) for the activation of the second N2O molecule necessary to complete the catalytic cycle by O-2 formation. The catalytic cycles for N2O decomposition over binuclear [Fe-II(mu-O)Fe-II](2+) and [Fe-III(mu-O-2)Fe-II](2+) species are interconnected. The catalytic cycle involves the interconversion of these species upon dissociation of N2O on the former complex. As the coordination of reactive Fe centers changes along the reaction coordinate, there are changes in the spin state of the complexes, which affect the overall potential energy diagram. These changes in spin multiplicities facilitate O-2 formation and desorption steps. Based on the DFT-computed potential energy diagrams, microkinetic model simulations were carried out to predict reaction rates and kinetic parameters. The rate of O-2 formation is much higher on binuclear sites than on mononuclear sites. For mononuclear sites, the apparent activation energy is similar to 180 kJ/mol, close to the barrier for dissociating a second N2O molecule. It is consistent with first-order behavior with respect to the partial pressure of N2O. Binuclear sites display much higher reactivity. At low temperature, O-2 desorption is rate controlling, whereas at higher temperatures, the rate is controlled by the two N2O dissociation reactions on [Fe-II(mu-O)Fe-II](2+) and [Fe-III(mu-O)(2)Fe-III](2+). This leads to first-order behavior with respect to N2O. An alternative path involving N2O adsorption and dissociation on [OFe(mu-O)(2)Fe](2+) is energetically favorable but does not contribute to the catalytic cycle because O-2 desorption from the [OFe(mu-O)(2)Fe](2+) intermediate is preferred over the activation of a third N2O molecule due to entropic reasons. (C) 2013 Elsevier Inc. All rights reserved.
关键词[WOS]: NITROUS-OXIDE DECOMPOSITION ;  HIGH-TEMPERATURE TREATMENT ;  FE-MFI ZEOLITES ;  INITIO MOLECULAR-DYNAMICS ;  CHEMICAL-VAPOR-DEPOSITION ;  DENSITY-FUNCTIONAL THEORY ;  TOTAL-ENERGY CALCULATIONS ;  SURFACE OXYGEN FORMATION ;  AUGMENTED-WAVE METHOD ;  ACTIVE-SITES
语种: 英语
原文出处: 查看原文
WOS记录号: WOS:000329881700035
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/119679
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Eindhoven Univ Technol, Inorgan Mat Chem Grp, NL-5600 MB Eindhoven, Netherlands
2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian, Peoples R China

Recommended Citation:
Li, Guanna,Pidko, Evgeny A.,Filot, Ivo A. W.,et al. Catalytic properties of extraframework iron-containing species in ZSM-5 for N2O decomposition[J]. JOURNAL OF CATALYSIS,2013,308:386-397.
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