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Download fileCatalytic Investigation of CO2 Chemical Fixation and the Knoevenagel Condensation Reaction for a TmIII–Organic Framework
journal contribution
posted on 14.12.2021, 20:35 authored by Tao Zhang, Zhengguo Zhang, Hongtai Chen, Xiutang Zhang, Qiaoling LiThe delicate combination of wave-like
[Tm2(CO2)6(OH2)2]n chains and [Tm(CO2)4(NO3)(OH2)] units with the aid
of 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine
(H5BDCP) generates one highly robust dual-channel material
of {[(CH3)2NH2]2[Tm3(BDCP)2(NO3)(OH2)3]·4DMF·2H2O}n (NUC-28) with excellent physicochemical properties
including solvent-free dual channels, a bigger specific surface area,
high porosity, water tolerance, and thermal stability. As far as we
know, NUC-28 is one scarcely reported nitrate-functionalized
microporous metal–organic framework (MOF) with NO groups
as Lewis base sites protruding on the inner surface of the channels.
Thanks to the coexistence of Lewis acid–base sites including
rich hexa-/hepta-coordinated Tm3+ ions, NO and
CO groups from μ1-η1:η1 NO3– and CO2–, and Npyridine atoms, NUC-28 displays high catalytic
activity in the cycloaddition reaction of epoxides and CO2 into related cyclic carbonates under mild, solvent-free reaction
conditions. In addition, Knoevenagel condensation reactions with aldehydes
and malononitrile as substrates could be greatly accelerated in the
presence of NUC-28. Hence, these catalytic results confirm
that the introduction of Lewis base sites of NO3– anions on open metal sites in MOFs could effectively enhance its
catalytic efficiency, which should be attributed to the recognized
synergistic effect of Lewis base–acid active sites.
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