Abstract
The exquisite combination of ZnII and HoIII generated the highly robust [ZnHo(CO2)6(OH2)]-based heterometallic framework of {[ZnHo(TDP)(H2O)]·5H2O·3DMF}n (NUC-30, H6TDP = 2,4,6-tri(2′,4′-dicarboxyphenyl)pyridine), which featured outstanding physicochemical properties, including honeycomb nanochannels, high porosity, large specific surface area, the coexistence of highly open Lewis acid–base sites, good thermal and chemical stability, and resistance to most organic solvents. Due to its extremely unsaturated metal tetra-coordinated Zn(ii) ions, hepta-coordinated Ho(iii) and high faveolate void volume (61.3%), the conversion rate of styrene oxide and CO2 into cyclic carbonates in the presence of 2 mol% activated NUC-30 and 5 mol% n-Bu4NBr reached 99% under the mild conditions of 1.0 MPa and 60 °C. Furthermore, the luminescence sensing experiments proved that NUC-30 could be used as a fast, sensitive and highly efficiency sensor for the detection of Fe3+ in aqueous solution. Therefore, these results prove that nanoporous MOFs assembled from pyridine-containing polycarboxylate ligands have wide applications, such as catalysis and as luminescent materials.
Highlights
IntroductionPorous metal–organic frameworks (MOFs), as a booming family of organic–inorganic hybrid materials, have aroused much interest owing to their potential applications as heterogeneous catalysts, gas separation and storage materials, biomedical and chemical sensors, electrochemical microelectrodes, etc. With the development of technology and social advancement, the highly optimized synthesis of targeted MOFs has been adopted and applied stepwise by combining functionalized organic linkers and special metal clusters to realize excellent functional characteristics including inherent porosity, large surface area, and active sites. far, numerous MOFs have been widely applied as a type of effective separation and catalytic material for the separation and chemical conversion of CO2, which has created the serious problem of global warming because of excessive emissions from modern enterprises and motorized tools. the mild reaction conditions of low temperature and pressure utilizing MOF catalysts are incomparable with other hetero- and homogeneous catalysts, for instance, zeolites, inorganic metal salts or oxides, ionic liquids, amine aqueous solutions, and polymerized organics
Numerous metal–organic frameworks (MOFs) have been widely applied as a type of effective separation and catalytic material for the separation and chemical conversion of CO2, which has created the serious problem of global warming because of excessive emissions from modern enterprises and motorized tools
Both types of alternately arranged nano-channels (I and II) in NUC-30 shaped by six rows of [ZnHo(CO2)6(H2O)] SBUs have an equal amount of exposed active metal sites, they could be discriminated from their different functionalized inner surfaces with free carboxyl oxygen atoms (C]O) and coordinated aqueous molecules (H2O)
Summary
Porous metal–organic frameworks (MOFs), as a booming family of organic–inorganic hybrid materials, have aroused much interest owing to their potential applications as heterogeneous catalysts, gas separation and storage materials, biomedical and chemical sensors, electrochemical microelectrodes, etc. With the development of technology and social advancement, the highly optimized synthesis of targeted MOFs has been adopted and applied stepwise by combining functionalized organic linkers and special metal clusters to realize excellent functional characteristics including inherent porosity, large surface area, and active sites. far, numerous MOFs have been widely applied as a type of effective separation and catalytic material for the separation and chemical conversion of CO2, which has created the serious problem of global warming because of excessive emissions from modern enterprises and motorized tools. the mild reaction conditions of low temperature and pressure utilizing MOF catalysts are incomparable with other hetero- and homogeneous catalysts, for instance, zeolites, inorganic metal salts or oxides, ionic liquids, amine aqueous solutions, and polymerized organics.. Reported Zn-MOFs based on tetra-coordinated Zn2+ ions with solventfree channels displayed good selective adsorption performances for the guest molecules of CO2 and catalyzed the chemical transformation of epoxides with CO2 into the corresponding alkyl carbonates. This is because the exposed active Zn2+ ions act as a strong Lewis acid to polarize and activate CO2 and the ring of ethylene oxide via coordination affinity.. At the end of the catalytic reaction, the heterogeneous catalyst NUC-30 was retrieved through simple centrifugation separation a er each reaction was complete, and cleaned with strong polar solvent of DMF and volatile solvent of acetone in sequence
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