Polyoxometalate-Based Metal–Organic Frameworks
for Selective Oxidation of Aryl Alkenes to Aldehydes
Posted on 2018-03-13 - 13:34
Polyoxometalates
(POMs) show considerable catalytic performance
toward the selective oxidation of alkenes to aldehydes, which is commercially
valuable for the production of pharmaceuticals, dyes, perfumes, and
fine chemicals. However, the low specific surface area of POMs as
heterogeneous catalysts and poor recyclability as homogeneous catalysts
have hindered their wide application. Dispersing POMs into metal–organic
frameworks (MOFs) for the construction of POM-based MOFs (POMOFs)
suggests a promising strategy to realize the homogeneity of heterogeneous
catalysis. Herein, we report two new POMOFs with chemical formulas
of [Co(BBTZ)2][H3BW12O40]·10H2O (1) and [Co3(H2O)6(BBTZ)4][BW12O40]·NO3·4H2O (2) (BBTZ
= 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene) for the selective oxidation
of alkenes to aldehydes. Compound 1 possesses a non-interpenetrated
three-dimensional (3D) cds-type open framework with
a 3D channel system. Compound 2 displays a 3D polyrotaxane
framework with one-dimensional channels along the [100] direction.
In the selective oxidation of styrene into benzaldehyde, compound 1 can achieve a 100% conversion in 4 h with 96% selectivity
toward benzaldehyde, which is superior to that of compound 2. A series of control experiments reveal that the co-role of [BW12O40]5– and Co2+ active
center as well as a more open framework feature co-promote the catalytic
property of the POMOFs in this case. This work may suggest a new option
for the development of POMOF catalysts in the selective oxidation
of alkenes.
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Ma, Yuanyuan; Peng, Haiyue; Liu, Jianing; Wang, Yonghui; Hao, Xiuli; Feng, Xiaojia; et al. (2018). Polyoxometalate-Based Metal–Organic Frameworks
for Selective Oxidation of Aryl Alkenes to Aldehydes. ACS Publications. Collection. https://doi.org/10.1021/acs.inorgchem.8b00282
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AUTHORS (9)
YM
Yuanyuan Ma
HP
Haiyue Peng
JL
Jianing Liu
YW
Yonghui Wang
XH
Xiuli Hao
XF
Xiaojia Feng
SK
Shifa Ullah Khan
HT
Huaqiao Tan
YL
Yangguang Li
KEYWORDS
BW 12 O 40surface areacompound 1alkeneBBTZcompound 24 hCompound 2 displaysAldehydes Polyoxometalatescontrol experiments3 D polyrotaxane frameworkPOM-based MOFsoxidationCompound 1Co 3Aryl Alkenes3 D channel systemframework feature co-promoteH 2 Ochemical formulasPOMOF catalystsDispersing POMsaldehydebenzaldehydeSelective Oxidation