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Preparation of a class of azo bond-rich covalent organic frameworks and their applications in proton conduction and fuel cells

A technology of covalent organic framework and aromatic azo, applied in fuel cells, circuits, electrical components, etc., can solve the problem of low proton conductivity

Active Publication Date: 2022-05-10
耀科新材料(苏州)有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Aiming at the low proton conductivity of traditional COFs, this application creatively synthesized a series of trihydroxy-substituted aromatic azo compounds (named Azo-R, R=NHBoc, NH 2 ,p-phenyl-NHBoc, CHO, B(OH) 2 , CN, CH 2 CN, etc.), and then used them as precursors to synthesize a series of highly crystalline, high specific surface junction, and stable new COFs (named NKCOF-1, -2, -3, -4, ...; NKCOF=Nankai covalent organicframeworks), these COFs contain a high density of azo and phenolic hydroxyl groups, and after loading phosphoric acid, these COFs exhibit good proton conductivity

Method used

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  • Preparation of a class of azo bond-rich covalent organic frameworks and their applications in proton conduction and fuel cells
  • Preparation of a class of azo bond-rich covalent organic frameworks and their applications in proton conduction and fuel cells
  • Preparation of a class of azo bond-rich covalent organic frameworks and their applications in proton conduction and fuel cells

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] The synthesis of a series of organic small molecule precursors rich in hydroxyl and azo groups, the specific implementation steps are as follows:

[0036] The new small molecular precursors containing high-density azo bonds mainly use the bond-forming reaction of azo. Contains amino-NH 2 The monomer (10 mmol) was dissolved in 20 mL of 1 molar hydrochloric acid, and NaNO was slowly added in an ice-water bath 2 (11mmol), after the addition, keep stirring in an ice-water bath for 1 hour. Next, trisphenol (3 mmol) was dissolved in 20.2 mL of 1M NaOH aqueous solution, and cooled to 0-5°C. Then it was slowly added dropwise into the previous reaction system, and after the dropwise addition was completed, the reaction was continued for 4 hours. A large amount of red-black solid was produced, filtered and dried to obtain the product (80% yield).

[0037] The synthesis of a series of new COFs, the specific implementation steps are as follows:

[0038] The synthesis of NKCOFs...

Embodiment 2

[0045] Example 2: Loading of NKCOFs phosphoric acid

[0046] 60 mg of NKCOFs powder was soaked in 5 M phosphoric acid aqueous solution for 12 hours, filtered, and then the solid was washed thoroughly with water until the eluent reached pH = 7, and then the resulting sample was dried at 120 °C for 24 hours to obtain dried phosphoric acid-loaded NKCOFs ( named H 3 PO 4 @NKCOFs). Selection of soaking time: Experiments have found that the soaking time is in the range of 0 to 12 hours. The longer the soaking time, the higher the proton conductivity. When the soaking time exceeds 12 hours, the proton conductivity will no longer increase. Thus choose 12 hours as the preparation H 3 PO 4 Soak time for @NKCOFs. Calculated phosphoric acid in H by thermogravimetry and other tests 3 PO 4 Final load in @NKCOFs.

Embodiment 3

[0047] Embodiment 3: the preparation of NKCOF film

[0048] NKCOF membranes can be prepared by powder compression and direct synthesis. Powder compression: take 50 mg of NKCOFs powder, and use an infrared mold to press it into a circular sheet with a diameter of 1.3 cm and a thickness of 200-400 μm under a pressure of 20 MPa. Direct synthesis: mix a certain amount of Azo-NH2, aldehyde, p-toluenesulfonic acid and water, grind it into a uniformly dispersed paste in a mortar, and then spread the paste evenly on a clean glass plate , reacted at 90 °C for 24 hours, washed with hot water and dried to obtain a crystalline, self-supporting COF membrane. In addition, the film can also be obtained by suction filtration after stripping, or the COF monomer can be dissolved in different solvents by the interfacial method, such as water phase and oil phase, and a high-quality COF film can be obtained by interfacial diffusion.

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Abstract

The present invention uses a step-by-step synthesis strategy to prepare a series of aromatic azo compound building blocks (named after Azo-R, R=NHBoc, NH 2 , p‑phenyl‑NHBoc, CHO, B(OH) 2 , CN, CH 2 CN, etc.), and then used them as precursors to synthesize a series of stable, highly crystalline and high specific surface novel covalent organic frameworks (COFs) materials. Through characterization, it is found that these COFs have high specific surface area and excellent chemical stability, and can be used in various common organic solvents (acetone, dichloromethane, DMF, etc.), concentrated hydrochloric acid (12M), concentrated alkali NaOH (12M), Stable in boiling water. In addition, they show good hydrophilicity and high water vapor adsorption capacity, which make this type of COFs an ideal proton-conducting material. After loading phosphoric acid, these COFs achieved ultra-high proton conductivity with a conductivity of 1.13×10 ‑ 1 S / cm, this value can be compared with the value of commercial Nafion (~1.1×10 ‑1 S / cm) comparable. These COFs can be easily fabricated into proton exchange membrane devices and applied to hydrogen-oxygen fuel cells.

Description

technical field [0001] The invention belongs to the field of proton exchange membrane fuel cells, and in particular relates to the preparation of a series of high-density azo bond-containing and highly crystalline novel covalent organic frameworks (covalent organic frameworks, COFs), and their application in proton conduction and fuel cells . Background technique [0002] At present, the world's energy is mainly supplied by the combustion of fossil fuels, but the exploitation and combustion of fossil fuels have brought a series of major environmental problems: such as the destruction of the ecological environment, air pollution, water pollution and so on. Moreover, as non-renewable resources, fossil fuels are increasingly depleted and cannot meet the growing energy demand. Therefore, it is imminent to find clean and renewable energy to replace fossil fuels. Hydrogen has attracted much attention as an ideal clean energy. Proton exchange membrane fuel cell technology has th...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G83/00H01M8/103
CPCC08G83/008H01M8/103H01M2008/1095Y02E60/50
Inventor 张振杰陈瑶杨毅
Owner 耀科新材料(苏州)有限公司
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