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The formation mechanism of Mo-methylidene species over Mo/HBeta catalysts for heterogeneous olefin metathesis: A density functional theory study
Guan, Jing1; Yang, Gang1; Zhou, Danhong1,2; Zhang, Weiping1; Liu, Xianchun1; Han, Xiuwen1; Bao, Xinhe1; Bao XH(包信和)
KeywordActive Sites Density Functional Calculations Mo/hbeta Catalysts Olefin Metathesis Oxidation States
Source PublicationJOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
2009-03-02
DOI10.1016/j.molcata.2008.10.044
Volume300Issue:1-2Pages:41-47
Indexed BySCI
SubtypeArticle
Department5
Funding Project502
Contribution Rank1;1
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Physical
WOS Research AreaChemistry
WOS KeywordPHOTOREDUCED SILICA-MOLYBDENA ; X-RAY-ABSORPTION ; ALUMINA CATALYSTS ; ZEOLITE-BETA ; ACID SITES ; CHEMISORBED CYCLOPROPANE ; COORDINATION-NUMBER ; CARBENE COMPLEXES ; DFT CALCULATIONS ; OXO BONDS
AbstractDensity Functional Theory (DFT) calculations were performed to optimize the Mo active sites in HBeta zeolite catalysts as well as to locate the reaction pathways to form the Mo-methylidene species. Two different Mo active sites. i.e., the oxidized (MoO2)-O-VI and its reduced form (MoO)-O-V(OH), were developed and incorporated into HBeta zeolites by replacing a pair of Bronsted acidic sites. The Mo-methylidene species were found to be produced through two elementary reaction steps, and the Mo-oxametallacyclobutanes were identified as the intermediates. The activation barriers of the decompositions of the oxametallacyclobutane intermediates (Step 2) were estimated to be higher than those of the ethene addition on the Mo active sites (Step 1). The oxidation states of the Mo centers exerted marked influences on the stabilities of the intermediates as well as oil the activation barriers and reaction heats of Steps 1 and 2, which were elucidated by the electronic properties of the O-b-ligands directly bonded to the Mo centers. Both free energy barriers and reaction heats have indicated that the whole processes of generating the Mo-methylidene species were preferred over the Mo(VI) rather than Mo(V) active site. Accordingly. the Mo(VI) active site was more efficient in catalyzing the formation of Mo-methylidene species in the heterogeneous Mo/HBeta catalytic systems. (C) 2008 Elsevier B.V. All rights reserved.
Language英语
URL查看原文
WOS IDWOS:000264013400007
Citation statistics
Cited Times:15[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/102263
Collection中国科学院大连化学物理研究所
Corresponding AuthorBao XH(包信和)
Affiliation1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China
2.Liaoning Normal Univ, Coll Chem & Chem Engn, Inst Chem Functionalized Mat, Dalian 116029, Peoples R China
Recommended Citation
GB/T 7714
Guan, Jing,Yang, Gang,Zhou, Danhong,et al. The formation mechanism of Mo-methylidene species over Mo/HBeta catalysts for heterogeneous olefin metathesis: A density functional theory study[J]. JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL,2009,300(1-2):41-47.
APA Guan, Jing.,Yang, Gang.,Zhou, Danhong.,Zhang, Weiping.,Liu, Xianchun.,...&包信和.(2009).The formation mechanism of Mo-methylidene species over Mo/HBeta catalysts for heterogeneous olefin metathesis: A density functional theory study.JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL,300(1-2),41-47.
MLA Guan, Jing,et al."The formation mechanism of Mo-methylidene species over Mo/HBeta catalysts for heterogeneous olefin metathesis: A density functional theory study".JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 300.1-2(2009):41-47.
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