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Acetylene cyclotrimerization catalyzed by TiO2 and VO2 in the gas phase: A DFT study
Ma, Yan-Ping; Xue, Wei; Wang, Zhe-Chen; Ge, Mao-Fa; He, Sheng-Gui
2008-04-24
Source PublicationJOURNAL OF PHYSICAL CHEMISTRY A
ISSN1089-5639
Volume112Issue:16Pages:3731-3741
AbstractDensity functional theory (DFT) calculations have been used to investigate acetylene cyclotrimerization catalyzed by titanium and vanadium dioxides. The calculated results illustrate that the overall process is highly favorable at room temperature from both thermodynamic and kinetic points of view. The mechanism Of C2H2 cyclotrimerization over MO2 (M = Ti, V) can be understood as four steps: (1) a four-membered ring (-O-M-C=C-) formation that coordinates and activates the first C2H2 molecule; (2) the second C2H2 insertion into the M-C bond to form a six-membered ring (-O-M-C=C-C=C-); (3) the third C2H2 insertion into the M-C bond to form an eight-membered ring (-O-M-C=C-C=C-C=C-); and (4) contraction of the eight-membered ring and benzene formation and desorption. All of the reaction steps are overall barrierless with respect to the separated reactants (MO2C2xH2x + C2H2, X = 0, 1, 2). This theoretical study predicts that the M=O double bond in MO2 is very catalytic toward the C2H2 cyclotrimerization. The metal center in this study can be considered always in the same +4 oxidation state (Ti4+ and V4+). In contrast, two-electron cycling of the metal center is present in the documented mechanism for the C2H2 cyclotrimerization. The C2H2 cyclotrimerization over the Ti atom and TiO molecule is also studied, and the documented mechanism applies in this case. The new mechanism is suggested to apply to reactions using titanium and vanadium oxides as catalysts.
DOI10.1021/jp711027z
Indexed BySCI
Language英语
WOS IDWOS:000255104800027
PublisherAMER CHEMICAL SOC
Citation statistics
Cited Times:32[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/64776
Collection中国科学院化学研究所
Corresponding AuthorHe, Sheng-Gui
AffiliationChinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing Natl Lab Mol Sci, Beijing 100080, Peoples R China
Recommended Citation
GB/T 7714
Ma, Yan-Ping,Xue, Wei,Wang, Zhe-Chen,et al. Acetylene cyclotrimerization catalyzed by TiO2 and VO2 in the gas phase: A DFT study[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2008,112(16):3731-3741.
APA Ma, Yan-Ping,Xue, Wei,Wang, Zhe-Chen,Ge, Mao-Fa,&He, Sheng-Gui.(2008).Acetylene cyclotrimerization catalyzed by TiO2 and VO2 in the gas phase: A DFT study.JOURNAL OF PHYSICAL CHEMISTRY A,112(16),3731-3741.
MLA Ma, Yan-Ping,et al."Acetylene cyclotrimerization catalyzed by TiO2 and VO2 in the gas phase: A DFT study".JOURNAL OF PHYSICAL CHEMISTRY A 112.16(2008):3731-3741.
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