DICP OpenIR
Subject Area物理化学
Catalytic properties of extraframework iron-containing species in ZSM-5 for N2O decomposition
Li, Guanna1,2; Pidko, Evgeny A.1; Filot, Ivo A. W.1; van Santen, Rutger A.1; Li, Can2; Hensen, Emie J. M.1; Li C(李灿); Emiel J.M. Hensen
KeywordFe/zsm-5 Dft Calculations Zeolite Reaction Mechanism Binuclear Complexes N2o Decomposition Microkinetic Modeling
Source PublicationJOURNAL OF CATALYSIS
2013-12-01
DOI10.1016/j.jcat.2013.08.010
Volume308Pages:386-397
Indexed BySCI
Cooperation Status
SubtypeArticle
Department5
Funding Project503
Contribution Rank待补充
WOS HeadingsScience & Technology ; Physical Sciences ; Technology
Funding Organization2,1 ; 2,1 ; 2,1 ; 2,1
WOS SubjectChemistry, Physical ; Engineering, Chemical
WOS Research AreaChemistry ; Engineering
WOS KeywordNITROUS-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
AbstractThe 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.
Language英语
Funding Organization2,1 ; 2,1 ; 2,1 ; 2,1
URL查看原文
WOS IDWOS:000329881700035
Citation statistics
Cited Times:24[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/119679
Collection中国科学院大连化学物理研究所
Corresponding AuthorLi C(李灿); Emiel J.M. Hensen
Affiliation1.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
GB/T 7714
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.
APA Li, Guanna.,Pidko, Evgeny A..,Filot, Ivo A. W..,van Santen, Rutger A..,Li, Can.,...&Emiel J.M. Hensen.(2013).Catalytic properties of extraframework iron-containing species in ZSM-5 for N2O decomposition.JOURNAL OF CATALYSIS,308,386-397.
MLA Li, Guanna,et al."Catalytic properties of extraframework iron-containing species in ZSM-5 for N2O decomposition".JOURNAL OF CATALYSIS 308(2013):386-397.
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