Zirconium-based MOF catalyst loaded with double active sites as well as preparation method and application of zirconium-based MOF catalyst

A MOF and dual-activity technology, which is applied in the field of zirconium-based MOF catalysts loaded with dual active sites and its preparation, can solve the problems of limited and rare MOF catalysts, and achieve high-efficiency catalytic activity, easy large-scale industrial production, and low cost. Effect

Active Publication Date: 2020-04-24
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, MOF catalysts equipped with metal nanoparticles and single-site metal catalytic active sites are still very rare.
[0005] In summary, the research on UiO-68 series MOFs as catalyst supports has made great progress, but the use of two different ligands to optimize its framework structure and carry bimetallic catalytic sites makes it a dual-functional catalyst. Activity studies are still limited

Method used

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  • Zirconium-based MOF catalyst loaded with double active sites as well as preparation method and application of zirconium-based MOF catalyst
  • Zirconium-based MOF catalyst loaded with double active sites as well as preparation method and application of zirconium-based MOF catalyst
  • Zirconium-based MOF catalyst loaded with double active sites as well as preparation method and application of zirconium-based MOF catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0051] Under a nitrogen atmosphere, 2 mmol of 2,5-dibromoaniline, 5 mmol of 4-methoxycarbonylphenylboronic acid, and 12 mmol of cesium fluoride were dissolved in 30 mL of tetrahydrofuran, and then 0.7 mL of Mole of palladium acetate and 1.5 mmol of triphenylphosphine were stirred at 60°C for 48 hours. After the reaction, the solvent was distilled off under reduced pressure to obtain a yellow crude product. The above crude product was purified by column chromatography (dichloromethane:ethyl acetate=40:1, volume ratio), and finally the pure product 2'-amino-[1,1':4',1"-triple Phenyl]-4,4"-dimethyl ester, yield 80%.

[0052] The H NMR spectrum of 2'-amino-[1,1':4',1"-terphenyl]-4,4"-dimethyl ester is as follows figure 1 shown.

[0053] Dissolve 2'-amino-[1,1':4',1"-terphenyl]-4,4"-dimethyl ester in 35 ml of tetrahydrofuran and stir, add potassium hydroxide aqueous solution (2mol / L) , stirred at 55 °C for 12 hours. Afterwards, the solvent was distilled off under reduced press...

Embodiment 2

[0062] Weigh 1 mmol of the product metal organic framework UiO-68-NH obtained in Example 1 2 -CH 3 Mix well with 3 mmol of salicylaldehyde in 30 ml of acetonitrile, sonicate at room temperature for 20 minutes, and then react at 75 °C for 8 hours, in the metal organic framework UiO-68-NH 2 -CH 3 The aldehyde-amine chelation coordination site is obtained on the ligand. After the reaction is completed, after cooling to room temperature, wash with fresh acetonitrile and ethanol to obtain a yellow precipitate, dry it in a vacuum oven, and prepare the metal organic framework UiO-68-NH 2 -CH 3 -sal.

[0063] Figure 5 It is the metal organic framework UiO-68-NH of the product obtained in Example 22 -CH 3 -sal dissolved in HNO 3 / DMSO (deuterated HNO 3 Mixed solvent with deuterated DMSO, in which deuterated HNO 3 10 μ L, DMSO 590 μ L), the proton nuclear magnetic resonance spectrogram obtained by nuclear magnetic resonance test, from this Figure 5 As can be seen in the meta...

Embodiment 3

[0065] With 1 mmole of the product metal-organic framework UiO-68-NH obtained in Example 2 2 -CH 3 -sal and 3 millimoles of palladium chloride were mixed uniformly in 30 milliliters of methanol, stirred at room temperature for 12 hours, and the Pd 2+ Coordinated to the chelation site, washed by centrifugation, and dried in vacuo to give the product Pd 2+ @UiO-68-NH 2 -CH 3 . Will Pd 2+ @UiO-68-NH 2 -CH 3 At a temperature of 200°C, 5% H 2 / N 2 After reduction in the atmosphere for 4 hours, the MOF loaded with Pd nanoparticles (abbreviated as Pd@UiO-68-NH 2 -CH 3 ).

[0066] Figure 6 It is the MOF (i.e. Pd@UiO-68-NH 2 -CH 3 ) thermogravimetric diagram, it can be seen from the thermogravimetric diagram that the product has good thermal stability, and the structure of the material begins to decompose at about 462°C. Figure 7 It is the MOF loaded with Pd nanoparticles synthesized in Example 3 (Pd@UiO-68-NH 2 -CH 3 ) X-ray diffraction pattern, as can be seen from ...

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Abstract

The invention discloses a zirconium-based MOF catalyst loaded with double active sites as well as a preparation method and an application of the zirconium-based MOF catalyst. The method comprises thefollowing steps: adding zirconium salt and an organic ligand into an organic solvent, taking organic acid as a regulator, and carrying out self-assembly reaction to obtain a metal organic framework; adding salicylaldehyde for aldehyde amine condensation to obtain chelating coordination sites, adding palladium salt, and performing coordination through an impregnation method; reducing the obtained MOF in hydrogen to obtain an MOF loaded with Pd nanoparticles; reacting MOF and zinc salt in an organic solvent, and obtaining the catalyst. The Pd-Zn-coated UiO-68-NH2-CH3 catalyst synthesized by thepreparation method disclosed by the invention has efficient catalytic activity in a tandem alcohol oxidation/aldehyde cyanosilylation reaction. According to the catalyst, a metal organic framework UiO-68-NH2-CH3 is constructed, Pd nanoparticles and Zn <2+> are loaded by taking the metal organic framework UiO-68-NH2-CH3 as a carrier, the loading capacity of the Pd nanoparticles is 4-8wt%, and the loading capacity of the Zn <2+> is 3-5wt%.

Description

technical field [0001] The invention relates to the field of organic catalysis and porous materials, in particular to a zirconium-based MOF catalyst loaded with dual active sites and its preparation method and application. Background technique [0002] As an emerging porous material, metal-organic frameworks (MOFs) have the characteristics of high porosity, large specific surface area, and diverse topological structures. Zirconium-based MOFs not only have good thermal stability, but also have good water stability and acid and alkali resistance. Among them, UiO-68 series MOFs are widely used in the design of organic reaction catalysts because of their high porosity and large specific surface area, and can effectively support catalytic sites through design. The literature Chem.Mater.2016, 28, 2573-2580 reported that proline was coordinated on the ligand of UiO-68 to obtain a MOF catalyst with high catalytic activity, which was applied to catalyze diastereoselective addition o...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07F7/18
CPCB01J31/1691B01J31/2217B01J31/2239B01J35/006B01J2531/26B01J2531/48B01J2531/824C07F7/188
Inventor 任颜卫岳成龙江焕峰
Owner SOUTH CHINA UNIV OF TECH
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