Catalytic properties of extraframework iron-containing species in ZSM-5 for N2O decomposition
文献类型：期刊论文
| 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 |
| 刊名 | journal of catalysis
 |
| 出版日期 | 2013-12-01 |
| 卷号 | 308页码:386-397 |
| 关键词 | Fe/ZSM-5 DFT calculations Zeolite Reaction mechanism Binuclear complexes N2O decomposition Microkinetic modeling |
| 产权排序 | 待补充 |
| 通讯作者 | 李灿 ; emiel j.m. hensen |
| 合作状况 | 英 |
| 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. |
| WOS标题词 | science & technology ; physical sciences ; technology |
| 学科主题 | 物理化学 |
| 类目[WOS] | chemistry, physical ; engineering, chemical |
| 研究领域[WOS] | chemistry ; engineering |
| 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 |
| 收录类别 | SCI |
| 资助信息 | 2，1 |
| 原文出处 | 397 |
| 语种 | 英语 |
| WOS记录号 | WOS:000329881700035 |
| 公开日期 | 2014-09-11 |
| 源URL | [http://159.226.238.44/handle/321008/119679]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 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 |
| 推荐引用方式 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,&Hensen, Emie J. M..(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. |
入库方式： OAI收割
来源：大连化学物理研究所
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