Amino- and Sulfo-Bifunctionalized Metal–Organic Frameworks: One-Pot Tandem Catalysis and the Catalytic Sites

Liu, Hui; Xi, Fu-Gui; Sun, Wei; Yang, Ningning; Gao, En‐Qing

doi:10.1021/acs.inorgchem.6b01057

Cited by 91 publications

(64 citation statements)

References 38 publications

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“…By employing mixed‐component strategies, new degrees of freedom in controlling of MOF properties are gained. The incorporation of an additional linker or metal may result in changes of the material properties, like adsorption properties, acid‐base behavior, thermal, and chemical stability, conductivity, flexibility or the emission and absorption of light …”

Section: Influences Of the Mixed‐component Concept On The Propertiesmentioning

confidence: 99%

Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks

Bitzer

Kleist

2019

Chemistry A European J

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In recent years, the synthesis of mixed‐metal and mixed‐linker metal–organic frameworks with multiple metals and/or linker molecules combined in one framework has become a growing field of interest. These mixed‐component or multivariate metal–organic framework materials provide the possibility to introduce multiple functionalities inside one framework. The interaction of guest molecules with different functionalities in the same material is a promising approach in the fields of gas storage, separation, catalysis and drug delivery. Furthermore, the combination of different components may lead to synergistic effects that cannot be achieved otherwise. These mixed‐component approaches open up new pathways to an even larger range of possible customizations in the field of metal–organic frameworks.

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Section: Influences Of the Mixed‐component Concept On The Propertiesmentioning

confidence: 99%

Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks

Bitzer

Kleist

2019

Chemistry A European J

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“…One‐pot sequential reactions have become an attractive field due to their high importance in organic syntheses . The advantages of these reactions include reduce the number of synthesis steps, simple purifications, high performance, high atom economy, reduce wastes, decrease reaction time and recovery capability.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of multifunctional polymer containing Ni‐Pd NPs via thiol‐ene reaction for one‐pot cascade reactions

Kalbasi

Mesgarsaravi

Gharibi

2019

Applied Organom Chemis

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Recently, acid–base bifunctional catalysts have been considered due to their abilities, such as the simultaneous activation of electrophilic and nucleophilic species and their high importance in organic syntheses. However, the synthesis of acid–base catalysts is problematic due to the neutralization of acidic and basic groups. This work reports a facial approach to solve this problem via the synthesis of a novel bifunctional polymer using inexpensive materials and easy methods. In this way, at the first step, heterogeneous poly (styrene sulfonic acid‐n‐vinylimidazole) containing pentaerythritol tetra‐(3‐mercaptopropionate) (PETMP) and trimethylolpropane trimethacrylate (TMPTMA) cross‐linkers were synthesized in the pores of a mesoporous silica structure using click reaction as a novel bifunctional acid–base catalyst. After that, Ni‐Pd nanoparticles supported on poly (styrenesulfonic acid‐n‐vinylimidazole)/KIT‐6 as a novel trifunctional heterogeneous acid–base‐metal catalyst was prepared. The prepared catalysts were characterized by various techniques like FT‐IR, TGA, ICP‐AES, DRS‐UV, TEM, FE‐SEM, EDS‐Mapping, and XRD. The synthesized catalysts were efficiently used as bifunctional/trifunctional catalysts for one‐pot, deacetalization‐Knoevenagel condensation and one‐pot, three‐step and a sequential reaction containing deacetalization‐Knoevenagel condensation‐reduction reaction. It is important to note that the synthesized catalyst showing high chemo‐selectivity for the reduction of nitro group, alkenyl double bond and ester group in the presence of nitrile. Moreover, it was found that the different nanoparticles including Ni, Pd, and alloyed Ni‐Pd showing different chemo‐selectivity and catalytic activity in the reaction.

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“…With diverse functionalization capability on both organic ligands and inorganic nodes, MOFs could be a great candidate for bridging the gap between homogeneous and crystalline heterogeneous catalysts with high porosity and abundant active sites [23][24][25].By tailoring the pore system in terms of shape and size of the pore, MOFs could introduce shape and size selectivity to the substrates [23,24]. For example, MIL-101 functionalized both with amino and sulfo groups [26] and JUC-199 with both open metal sites (Zn 2+ ) and basic sites (-NH 2 ) [3] was used to catalyze the one-pot deacatalization-Knoevenagel condensation in the presence of organic solvent. Nevertheless, the solvent-free tandem reaction catalyzed by MOFs was rarely evaluated.MOFs with highly tunable inorganic building units especially with the easier integration of different metal cations into the same structure can be a great advantage for their applications [27][28][29] such as catalysis and gas adsorption and separation [30][31][32].…”

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confidence: 99%

Bifunctional Heterometallic Metal-Organic Frameworks for Solvent-Free Heterogeneous Cascade Catalysis

2020

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A family of heterometallic metal-organic frameworks (MOFs) (CPM200s) harmoniously coexisting as Lewis acids and base (azo) sites were prepared. Seven CPM200s were employed as multifunctional heterogeneous cascade catalysts for the one-pot deacetalization-Knoevenagel reaction in a solvent-free system. Benefiting from the cooperation between Lewis acids from the open metal sites and base sites from the ligands, the CPM200s showed high activity and selectivity for the tandem reaction. The heterometallic 3D porous framework reported here not only offers a combination of two opposite active sites in the same framework of materials but also increases mass transfer of the substrate, thus maximizing the efficiency and substrate selectivity of the bifunctional catalysts. The CPM200s showed the highest turnover frequency (TOF), outperforming that of the reported MOFs in tandem with the deacetalization-Knoevenagel reaction. A strong correlation between the TOF and charge-to-radius ratio (z/r) of metal ions in the CPM200s was observed for the first time. The bifunctional CPM200s catalysts can be reused five times without significant loss of activity.Catalysts 2020, 10, 309 2 of 11 tailorable and accessible active sites, are actively used for heterogeneous catalysis [20][21][22]. With diverse functionalization capability on both organic ligands and inorganic nodes, MOFs could be a great candidate for bridging the gap between homogeneous and crystalline heterogeneous catalysts with high porosity and abundant active sites [23][24][25].By tailoring the pore system in terms of shape and size of the pore, MOFs could introduce shape and size selectivity to the substrates [23,24]. For example, MIL-101 functionalized both with amino and sulfo groups [26] and JUC-199 with both open metal sites (Zn 2+ ) and basic sites (-NH 2 ) [3] was used to catalyze the one-pot deacatalization-Knoevenagel condensation in the presence of organic solvent. Nevertheless, the solvent-free tandem reaction catalyzed by MOFs was rarely evaluated.MOFs with highly tunable inorganic building units especially with the easier integration of different metal cations into the same structure can be a great advantage for their applications [27][28][29] such as catalysis and gas adsorption and separation [30][31][32]. In addition to the flexible inorganic building units, organic ligands can also be controlled and tuned to further enhance the material properties. For example, MOFs containing both basic sites from the ligands part and Lewis acid sites from the metallic nodes possessing unsaturated open metal sites (OMSs) can potentially be integrated together. The synthesized MOFs could be used as bifunctional heterogeneous catalysts for one-pot tandem reactions [33][34][35]. Recently, a group of heterometallic MOFs [(M III M II 2 (OH)(ABTC) 1.5 (H 2 O) 3 ) (ABTC = full form of this ligand) with clear mention of the trimeric (M II 2 M III (µ 3 -OH)(CO 2 ) 6 ) clusters] with combinations of trivalent M III (Fe 3+ , V 3+ , Sc 3+ ) and divalent M II (Mg 2+ , Mn 2+ , Co 2+ ...

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Amino- and Sulfo-Bifunctionalized Metal–Organic Frameworks: One-Pot Tandem Catalysis and the Catalytic Sites

Cited by 91 publications

References 38 publications

Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks

Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks

Synthesis of multifunctional polymer containing Ni‐Pd NPs via thiol‐ene reaction for one‐pot cascade reactions

Bifunctional Heterometallic Metal-Organic Frameworks for Solvent-Free Heterogeneous Cascade Catalysis

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