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Hollow metal organic framework capsule material for coating homogeneous catalyst as well as preparation method and application thereof

A metal-organic framework and homogeneous catalyst technology, applied in the field of nanomaterials, can solve the problems of composite catalyst activity, selectivity inferior to homogeneous molecular catalysts, molecular guest distortion, etc., to achieve heterogeneous and maintain activity effects

Active Publication Date: 2020-07-21
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] The prior art discloses various methods for coating homogeneous catalysts, such as direct embedding of homogeneous molecular catalysts in the intrinsic pores of metal-organic frameworks , this method is to directly confine the guest molecules in the narrow pores of the metal-organic framework. The narrow pore space brings significant mass transfer resistance to the catalytic process, and even leads to distortion of the molecular guest, etc., which in turn leads to the final composite catalyst. Molecular catalysts with far less activity and selectivity than homogeneous ones

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  • Hollow metal organic framework capsule material for coating homogeneous catalyst as well as preparation method and application thereof
  • Hollow metal organic framework capsule material for coating homogeneous catalyst as well as preparation method and application thereof
  • Hollow metal organic framework capsule material for coating homogeneous catalyst as well as preparation method and application thereof

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preparation example Construction

[0052] The present invention also provides a method for preparing the above-mentioned hollow metal-organic framework capsule material for coating a homogeneous catalyst, comprising the following steps:

[0053] a. Pre-preparing a hollow inorganic template formed by stacking layered double oxyhydroxides;

[0054] b. Soak the hollow inorganic template in the homogeneous catalyst solution, make the hollow inorganic template adsorb the homogeneous catalyst into the cavity of the hollow inorganic template, and obtain a composite of homogeneous catalyst / hollow inorganic template Material;

[0055] c. Mix the ligand solution of the metal-organic framework material with the homogeneous catalyst / hollow inorganic template composite material, and then add the metal salt solution of the metal-organic framework material to react to obtain a hollow template for coating the homogeneous catalyst. Metal-organic framework capsule materials.

[0056] The present invention firstly prepares a ho...

Embodiment 1

[0093] The preparation method of the metal-organic framework capsule material guided by the template of this example is carried out as follows:

[0094] a, preparing a hollow inorganic template;

[0095] Coordination of cobalt nitrate hexahydrate and 2-methylimidazole in methanol solution to obtain a metal organic framework material; wherein, the ratio of the cobalt salt, ligand and methanol solution is 747mg: 984mg: 150mL;

[0096] The metal-organic framework material is refluxed in an ethanol solution of cobalt nitrate for 2 hours, and then cooled, washed with ethanol and aged in an ethanol solution to prepare a hollow inorganic template.

[0097] Wherein the ethanol solution of cobalt nitrate required for the reflux treatment has a concentration of 4 mg / mL, a solvent volume of 75 mL, a reflux temperature of 90° C., and a reflux time of 2 h.

[0098] Wherein the hollow inorganic template prepared above is soaked in 20 mL of ethanol solution and left to age. Subsequent operat...

Embodiment 2

[0109] In this embodiment, the template-assisted encapsulation method of dye molecules of different sizes in the metal-organic framework capsule material is prepared according to the following steps:

[0110] a. The hollow inorganic template adsorbs soluble molecules, including large-sized dye molecules (Coomassie Brilliant Blue R 250 , referred to as R 250 , with a molecular weight of 824) and small-sized organic molecules (n-octylamine, with a molecular weight of 129); the ratio of large-sized dye molecules to small-sized organic molecules is 1mg: 0.5mL.

[0111] Wherein, the preparation method of the hollow inorganic template is the same as in Example 1;

[0112] The hollow inorganic template is soaked in a soluble molecule solution for 2 hours at room temperature.

[0113] b. Growth metal-organic framework shell materials guided by hollow inorganic templates;

[0114] The specific method is:

[0115] Mix the hollow inorganic template adsorption soluble molecular compos...

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Abstract

The invention provides a hollow metal organic framework capsule material for coating a homogeneous catalyst. The hollow metal organic framework capsule material comprises a hollow inorganic template;a homogeneous catalyst dispersed in the hollow inorganic template; and a metal organic framework shell layer covering the surface of the hollow inorganic template. The metal organic framework materialconfinement homogeneous catalyst with a hollow structure is utilized, the large cavity can contain more guest molecules and avoid mass transfer resistance and the like caused by the fact that the guest molecules block pore channels, and a homogeneous catalysis environment can be simulated to maintain the activity and selectivity of original active guest molecules to the maximum extent. In addition, the metal organic framework shell layer also endows the guest molecular catalyst with specific properties of a metal organic framework material, including a substrate enrichment function, a size selectivity catalysis function and a host-guest synergistic catalysis function.

Description

technical field [0001] The invention belongs to the technical field of nanomaterials, and in particular relates to a hollow metal-organic framework capsule material for coating a homogeneous catalyst, a preparation method and application thereof. Background technique [0002] How to solve the problems of difficult recovery of soluble catalysts / homogeneous catalysts and easy polymerization deactivation has received more and more attention. Using porous materials to confine homogeneous catalysts to make them heterogeneous is a promising strategy. This requires a porous material with a large pore space to accommodate the guest molecule catalyst; but small openings inhibit the loss of the guest molecule, and at the same time allow the catalytic substrate / product to freely enter and exit the porous material, thereby realizing a heterogeneous homogeneous catalyst without It affects the contact between the guest and the substrate of the homogeneous catalyst and the mass transfer p...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22B01J31/28B01J35/02C07C253/30C07C255/41C07D317/36B01J35/00
CPCB01J31/1691B01J31/1815B01J31/183B01J31/28C07D317/36C07C253/30C07C45/38B01J2531/26B01J2531/16B01J2531/845B01J35/00B01J35/30C07C255/41C07C47/54
Inventor 江海龙蔡国瑞
Owner UNIV OF SCI & TECH OF CHINA
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