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Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof

A technology of metal-organic framework and proton exchange membrane, which is applied in the direction of electrochemical generators, fuel cells, electrical components, etc., can solve the problems of high preparation costs, and achieve the effects of high structural stability, excellent capture effect, and strong water retention capacity

Active Publication Date: 2021-09-03
HUAZHONG UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The inventors of the present invention obtained "Polymer Hybrid Proton Exchange Membrane with Modified Metal-Organic Framework Structure and Its Preparation Method" in the previous research (please refer to the Chinese patent document with application number 201610552499), although it also involves polymer hybridization Proton exchange membrane and its preparation method, but the examples of this previous patent show that the proton conductivity of the prepared proton exchange membrane at 90°C and 95% RH is the highest at 0.303S / cm; at 120°C, anhydrous The highest proton conductivity under the condition is 3.403mS / cm, there is still room for improvement
Moreover, since this previous research result requires the use of graphene oxide (GO), the preparation of GO requires concentrated acid to oxidize graphite and repeated cleaning after oxidation, and the preparation cost of GO is relatively high, which still has a large actual improvement needs

Method used

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  • Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof
  • Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof
  • Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] 1. Weigh 5.94g Zn(NO 3 ) 2 ·6H 2 O and 4.92g 2-methylimidazole, it was added in 400mL of methanol, ultrasonically dispersed into a uniform ZIF-8 precursor solution, it was transferred to the flask, then at 25 ° C for 16h of continuous stirring reaction, the The reaction product was separated by centrifugation, washed with fresh methanol solvent (can be washed several times according to the actual situation), and then placed in a vacuum oven at 50°C for 6 hours to obtain the metal organic framework ZIF-8.

[0039] 2. Weigh 400mg ZIF-8 and place it in 300mL tannic acid aqueous solution (4g / L) to etch for 15min, centrifuge to separate the product, clean it with fresh methanol solvent, and then dry it in a vacuum oven at 50°C for 5h, that is Obtain hollow ZIF-8 (TZIF-8); (since the main hydrolysis product of tannic acid is trihydroxybenzoic acid, so in addition to using tannic acid, monohydroxybenzoic acid, dihydroxybenzoic acid or trihydroxybenzoic acid can also be used ...

Embodiment 2

[0044] 1. Weigh 5.94g Zn(NO 3 ) 2 ·6H 2 O and 4.92g 2-methylimidazole, it was added in 400mL of methanol, ultrasonically dispersed into a uniform ZIF-8 precursor solution, it was transferred to the flask, then at 25 ° C for 16h of continuous stirring reaction, the The reaction product was separated by centrifugation, washed with fresh methanol solvent (can be washed several times according to the actual situation), and then placed in a vacuum oven at 50°C for 6 hours to obtain the metal organic framework ZIF-8.

[0045] 2. Weigh 400mg ZIF-8 and place it in 300mL tannic acid aqueous solution (4g / L) to etch for 15min, centrifuge to separate the product, clean it with fresh methanol solvent, and then dry it in a vacuum oven at 50°C for 5h, that is Obtain hollow ZIF-8 (TZIF-8);

[0046] 3. Weigh 100mg TZIF-8 into 200mL Tris buffer solution (pH 8.5), ultrasonically disperse it evenly, then add 50mg dopamine hydrochloride to it, put it in an ice-water bath and ultrasonically for ...

Embodiment 3

[0050] 1. Weigh 5.94g Zn(NO 3 ) 2 ·6H 2 O and 4.92g 2-methylimidazole, it was added in 400mL of methanol, ultrasonically dispersed into a uniform ZIF-8 precursor solution, it was transferred to the flask, then at 25 ° C for 16h of continuous stirring reaction, the The reaction product was separated by centrifugation, washed with fresh methanol solvent (can be washed several times according to the actual situation), and then placed in a vacuum oven at 50°C for 6 hours to obtain the metal organic framework ZIF-8.

[0051] 2. Weigh 400mg ZIF-8 and place it in 300mL tannic acid aqueous solution (4g / L) to etch for 15min, centrifuge to separate the product, clean it with fresh methanol solvent, and then dry it in a vacuum oven at 50°C for 5h, that is Obtain hollow ZIF-8 (TZIF-8);

[0052] 3. Weigh 100mg TZIF-8 into 200mL Tris buffer solution (pH 8.5), ultrasonically disperse it evenly, then add 50mg dopamine hydrochloride to it, put it in an ice-water bath and ultrasonically for ...

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Abstract

The invention belongs to the technical field of membranes, and discloses a polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof. The preparation comprises the following steps: (1) reacting metal salt with ligand to obtain a corresponding metal organic framework MOF; (2) etching the MOF in an aqueous solution of acid to obtain a hollow metal organic framework H-MOF; (3) putting the H-MOF into a buffer solution of dopamine hydrochloride, and stirring and reacting to obtain a polydopamine modified hollow metal organic framework H-MOF-D; and (4) adding the H-MOF-D into the sulfonated polymer solution to form a membrane casting solution and a membrane material, and soaking the membrane material in hydrogen peroxide, acid and deionized water to obtain the polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane. By improving the structure and composition of key functional components in the proton exchange membrane, the obtained proton exchange membrane has excellent proton conductivity under high and low humidity conditions.

Description

technical field [0001] The invention belongs to the field of membrane technology, and more specifically relates to a polydopamine-modified hollow metal organic framework (H-MOF-D) modified polymer hybrid proton exchange membrane and its preparation. In the present invention, the metal organic framework is denoted as MOF, the hollow metal organic framework is denoted as H-MOF, and the polydopamine-modified hollow metal organic framework is denoted as H-MOF-D. Background technique [0002] Proton exchange membrane fuel cell has the advantages of no pollution and high efficiency. It has become one of the most competitive alternative power sources for internal combustion engines, and has attracted extensive attention from industry and academia. As one of the core components of a proton exchange membrane fuel cell, the proton exchange membrane not only provides a channel for proton migration and transfer, but also effectively blocks the leakage of fuel between the anode and catho...

Claims

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Application Information

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IPC IPC(8): H01M8/1069H01M8/1067C08G83/00
CPCH01M8/1069H01M8/1067C08G83/008Y02E60/50
Inventor 刘宏芳饶壮李广芳
Owner HUAZHONG UNIV OF SCI & TECH
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