Highly efficient multi-site synergistic catalysis of a polyoxovanadate-based metal-organic framework for benzylic C-H bond oxidation

Dang, Tian-Yi1; Li, Run-Han1; Tian, Hong-Rui2; Guan, Wei1; Lu, Ying1; Liu, Shu-Xia1

2022-07-01

10.1039/d2ta03886b

Journal of Materials Chemistry A   影响因子和分区

2050-7488

2050-7496

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.

SCI ; EI

英语

其他

National Natural Science Foundation of China["22172022","22071019","21872021"]

Chemistry ; Energy & Fuels ; Materials Science

Chemistry, Physical ; Energy & Fuels ; Materials Science, Multidisciplinary

WOS:000827058800001

ROYAL SOC CHEMISTRY

20223112468372

Catalyst activity ; Catalytic oxidation ; Ketones ; Metal-Organic Frameworks ; Organic polymers ; Oxidants

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

Web of Science

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

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.

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.

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.