Title | Highly efficient multi-site synergistic catalysis of a polyoxovanadate-based metal-organic framework for benzylic C-H bond oxidation |
Author | |
Corresponding Author | Lu, Ying; Liu, Shu-Xia |
Publication Years | 2022-07-01
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DOI | |
Source Title | |
ISSN | 2050-7488
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EISSN | 2050-7496
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Volume | 10Pages:16514-16523 |
Abstract | The selective oxidation of C-H bonds of benzylic compounds to synthesize high-value-added ketones remains a challenge under mild conditions, and the ambiguity of its oxidation mechanism limits the further development of this field. In this work, we construct a polyoxometalate-based metal-organic framework (POMOF), [(Cu2CuII)-Cu-I(bix)(2)]{V4O12} (1, bix = 1,4-bis(imidazole-1-ylmethyl)benzene), successfully achieving the efficient oxidation catalysis of various benzylic compounds with outstanding conversion, selectivity and durability under mild conditions. Our experimental studies suggest that the highly catalytic activity of 1 derives from its attractive structure with multiple active sites, which consists of VV centers in a unique U-type {V4O12}(4-) ({V-4}) cluster and Cu-I and Cu-II centers bridged to the {V-4} cluster. Importantly, further theoretical calculations indicate that there exists synergistic catalysis between Cu-I/{V-4} sites and Cu-II/{V-4} sites for 1 as catalyst in the oxidation of benzylic compounds, where the {V-4} cluster mainly provides deprotonation and oxidation sites, and the CuI site plays a role in the reduction of the oxidant, while the Cu-II site plays a role in the adsorption of the oxidant. This is the first POMOF whose catalytic mechanism towards the oxidation of benzylic C-H bonds is deeply studied through the combination of experiments and theoretical calculations, providing a new perspective for the design of related catalysts. |
URL | [Source Record] |
Indexed By | |
Language | English
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SUSTech Authorship | Others
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Funding Project | National Natural Science Foundation of China["22172022","22071019","21872021"]
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WOS Research Area | Chemistry
; Energy & Fuels
; Materials Science
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WOS Subject | Chemistry, Physical
; Energy & Fuels
; Materials Science, Multidisciplinary
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WOS Accession No | WOS:000827058800001
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Publisher | |
EI Accession Number | 20223112468372
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EI Keywords | Catalyst activity
; Catalytic oxidation
; Ketones
; Metal-Organic Frameworks
; Organic polymers
; Oxidants
|
ESI Classification Code | Air Pollution Control:451.2
; Metallurgy:531.1
; Chemical Reactions:802.2
; Chemical Agents and Basic Industrial Chemicals:803
; Chemical Products Generally:804
; Organic Compounds:804.1
; Organic Polymers:815.1.1
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Data Source | Web of Science
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Citation statistics |
Cited Times [WOS]:6
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Document Type | Journal Article |
Identifier | http://kc.sustech.edu.cn/handle/2SGJ60CL/359461 |
Department | Department of Chemistry 深圳格拉布斯研究院 |
Affiliation | 1.Northeast Normal Univ, Coll Chem, Minist Educ, Key Lab Polyoxometalate & Reticular Mat Chem, Changchun 130024, Jilin, Peoples R China 2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China |
Recommended Citation GB/T 7714 |
Dang, Tian-Yi,Li, Run-Han,Tian, Hong-Rui,et al. Highly efficient multi-site synergistic catalysis of a polyoxovanadate-based metal-organic framework for benzylic C-H bond oxidation[J]. Journal of Materials Chemistry A,2022,10:16514-16523.
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APA |
Dang, Tian-Yi,Li, Run-Han,Tian, Hong-Rui,Guan, Wei,Lu, Ying,&Liu, Shu-Xia.(2022).Highly efficient multi-site synergistic catalysis of a polyoxovanadate-based metal-organic framework for benzylic C-H bond oxidation.Journal of Materials Chemistry A,10,16514-16523.
|
MLA |
Dang, Tian-Yi,et al."Highly efficient multi-site synergistic catalysis of a polyoxovanadate-based metal-organic framework for benzylic C-H bond oxidation".Journal of Materials Chemistry A 10(2022):16514-16523.
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