One Robust Microporous TmIII–Organic Framework for Highly Catalytic Activity on Chemical CO2 Fixation and Knoevenagel Condensation
- 31 December 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 60 (2), 1028-1036
- https://doi.org/10.1021/acs.inorgchem.0c03134
Abstract
In terms of documented references, multifunctional MOFs with high catalytic performance could be constructed from the combination of metal cations and polycarboxyl-pyridine ligands, which could efficiently endow crystallized porous frameworks with the coexisting Lewis acid-base properties. Thus, by employing a ligand-directed synthetic strategy, the exquisite combination of wave-like inorganic chains of [Tm(CO2)3(OH2)]n and mononuclear units of [Tm(CO2)4(OH2)2] with the aid of the specially designed ligand of 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (H5BDCP) generates one highly robust microporous framework of {(Me2NH2)[Tm3(BDCP)2)(H2O)3]·4DMF·H2O}n (simplified as NUC-25), which contains near-rectangular nanochannels and large solvent-residing voids. Furthermore, the activated state of NUC-25 with the removal of associated water molecules is a rarely reported bifunctional heterogeneous catalyst due to the coexistence of Lewis acid-base sites including 6-coordinated Tm3+ ions, uncoordinated carboxyl oxygen atoms, and Npyridine atoms. Just as expected, NUC-25 exhibits greatly high catalytic activity for the cycloaddition reaction of epoxides with CO2 into alkyl cyclic carbonates under bland solvent-free conditions, which should be ascribed to the polarity of nitrogen-containing pyridine heterocycles as Lewis base sites on the inner surface of nano-caged voids except for recognized Lewis acid sites of rare earth cations. Moreover, the excellent pore-size-dependent catalytic property for Knoevenagel condensation reactions confirms that NUC-25 can be viewed as a recyclable bifunctional heterogeneous catalyst. Therefore, these results strongly demonstrate that microporous MOFs assembled from pre-designed polycarboxyl-heterocyclic ligands display better catalytic performance not only for chemical CO2 fixation but also for Knoevenagel condensation reactions.Keywords
Funding Information
- National Natural Science Foundation of China (21101097, 21801230)
- Key Laboratory of Laser and Infrared System, Shandong University (2019-LISKFJJ-005)
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