Preparation method of core-shell type metal organic framework heterogeneous composite material
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A metal-organic framework and composite material technology, applied in the field of preparation of core-shell PBAs@ZIFs heterocomposite materials, can solve problems such as lattice mismatch
Inactive Publication Date: 2017-12-22
TIANJIN POLYTECHNIC UNIV
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[0006] The purpose of the present invention is to solve the lattice mismatch problem existing in the construction of core-shell metal-organic framework heterogeneous composite materials, and provides a preparation method of core-shell type PBAs@ZIFs heterogeneous composite materials. Vinylpyrrolidone (PVP) or sodium citrate (Na 3 Cit) is modified on the surface of PBAs crystals as the encapsulation medium, and the modified PBAs crystals are dispersed in the ZIFs precursor solution, and the PBAs are encapsulated in the ZIFs crystals by temperature-controlled ultrasound.
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Embodiment 1
[0022] A method for preparing a core-shell metal-organic framework heterogeneous composite material Ni-Co PBAs@Co-Zn ZIFs, the core of the composite material is Prussian blue-like Ni-Co PBAs, and the outer shell is Co-Zn ZIFs, a zeolite imidazolate framework material. The synthesis steps are as follows:
[0023] 1) Preparation of Ni-Co PBAs crystals
[0024] 1mmol K 3 [Co(CN) 6 ] was added to 20mL deionized water to fully dissolve to make solution A, and another 3mmolNa 3 Cit and 3 mmol NiCl 2 ·6H 2 O. Dissolve in 20mL deionized water to prepare solution B, mix the two slowly and keep stirring, age at room temperature for 24 hours, filter the precipitate, wash with deionized water and absolute ethanol for 3 times, and then incubate at 60°C Vacuum drying for 12 hours to obtain Prussian blue-like crystal Ni-Co PBAs;
[0026] Add 10 mg of the Prussian blue crystal Ni-...
Embodiment 2
[0030] Preparation of core-shell metal-organic framework heterogeneous composite Fe-Co PBAs@Co-Zn ZIFs, the core of the composite material is Prussian blue-like Fe-Co PBAs, and the outer shell is Co-Zn ZIFs. The synthesis steps are as follows:
[0031] 1) Preparation of Prussian blue-like Fe-Co PBAs
[0032] 1mmol K 3 [Co(CN) 6 ] was dissolved in 20mL deionized water to prepare a solution, and another 0.06mmol PVP and 3mmolFeSO 4 ·7H 2 O was added to 20 mL of deionized water to fully dissolve, and the two solutions were slowly mixed and stirred continuously, aged at room temperature for 24 hours, and the precipitate was filtered, washed with deionized water and absolute ethanol three times, and then heated at 60 °C Vacuum drying for 12 hours to obtain Prussian blue crystal Fe-Co PBAs;
[0034] Add 10 mg of the above-prepared Prussian blue crystals into 15 mL of meth...
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Abstract
The invention relates to a preparation method of a core-shell type metal organic framework heterogeneous composite material, in particular to a preparation method of a core-shell type PBAs@ZIFs heterogeneous composite material formed by using metal zeolite-imidazolate frameworks (ZIFs) to wrap and encapsulate Prussian blue analogs (PBAs). The preparation method includes: dissolving K3[Co(CN)6], divalent metal salt and polyvinyl pyrrolidone (PVP) or sodium citrate (Na3Cit) into deionized water, and aging at room temperature to obtain PBAs crystals; dispersing the prepared PBAs crystals into the precursor solution of ZIFs, and performing temperature-control ultrasonic treatment to obtain the PBAs@ZIFs heterogeneous composite material. The preparation method has the advantages that the PVP or the Na3Cit is ingeniously modified on the surfaces of the PBAs crystals to serve as the wrapping and encapsulating medium, the core-shell type metal organic framework heterogeneous composite material is simply and fast prepared by using the temperature-control ultrasonic treatment method, and the core-shell type metal organic framework heterogeneous composite material has the advantages of two MOF materials including the ZIFs and the PBAs and can be used as the high-effect catalyst of multi-metal synergistic effects.
Description
technical field [0001] The invention relates to a core-shell type metal-organic framework heterogeneous composite material, in particular to a core-shell type PBAs@ZIFs heterogeneity formed by encapsulating and encapsulating Prussian blue crystals (PBAs) with metal zeolite imidazolate framework materials (ZIFs) Methods of preparation of composite materials. Background technique [0002] Metal-organic frameworks (MOFs) are porous polymers formed by the self-assembly of inorganic metal ions and organic ligands through coordination. It has rich topology, tunable pore size, highly ordered pore structure and highly controllable surface functional groups. Due to their excellent properties, MOFs have shown great application potential in gas storage, sample separation, sensing, biomedicine and other fields. [0003] Zeolite imidazolate framework materials (ZIFs) are a class of MOF materials. Because of their large specific surface area, adjustable pore size, excellent thermal and ...
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