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MOF-SO3H@GO modified polymer hybrid proton exchange membrane and preparation method thereof

A technology of MOF-SO3H and polymers, which is applied in the direction of electrochemical generators, climate sustainability, and final product manufacturing, can solve the problems of composite membrane proton conductivity decline, proton conductivity not improved, and particles easy to agglomerate, etc. Achieve the effect of good industrial production basis, improved proton conductivity, and simple operation process

Inactive Publication Date: 2017-03-29
FUDAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

For example: "Chemical Communication" (Chemical Communication, 2013, 49, 143-145) reported that Fe-MIL-101-NH 2 Fe-MIL-101-NH was prepared by doping in sulfonated 2,6-dimethyl-p-polyphenylene oxide (SPPO) 2 Modified proton exchange membrane, the proton conductivity of the membrane is 0.1 S / cm at 25 ℃, 98% RH (relative humidity), which has a certain improvement compared with the unmodified SPPO (0.08 S / cm) membrane, but the improvement Not obvious. "Journal of Materials Chemistry A" (Journal of Materials Chemistry A 2015 (3) 15838-15842 ) reported that ZIF-8@GO was doped into Nafion to prepare ZIF-8@GO modified proton exchange membrane. Under the conditions of 120°C and 40% RH, the proton conductivity of the membrane reaches 0.28 S / cm, but the proton conductivity does not increase when the humidity is increased.
"Energy" (Journal of Power Sources 262 (2014) 372-379) reported that (MIL (101) Cr)-SO 3 (MIL (101) Cr)-SO 3 The H-modified proton exchange membrane has a proton conductivity of 0.306 S / cm at 75 °C and 100% RH, which is significantly improved compared with the unmodified SPEEK membrane, but when the particle addition reaches 10%, the particles are easy to agglomerate , the proton conductivity of the composite membrane decreased

Method used

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  • MOF-SO3H@GO modified polymer hybrid proton exchange membrane and preparation method thereof
  • MOF-SO3H@GO modified polymer hybrid proton exchange membrane and preparation method thereof
  • MOF-SO3H@GO modified polymer hybrid proton exchange membrane and preparation method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024]1. Ultrasonic dispersion of 150 mg GO in 45 mL of N,N-dimethylacetamide (DMA), then weighed 1000 mg of zirconium oxychloride octahydrate and 830 mg of sodium 2-sulfonic acid terephthalate were added to the above dispersion , then add 11.7mL of formic acid, and ultrasonically disperse. Transfer it to a 100 mL polytetrafluoroethylene liner, cover the lid and put it into the reactor to seal it tightly, then place it in a constant temperature oven at 150 °C for 24 h, and separate the reaction product by centrifugation. Wash continuously with fresh DMF solvent, and then with fresh CH 3 OH was washed several times, and the centrifuged product was finally placed in an oven at 50 °C for 6 hours to obtain MOF-SO 3 H@GO composite particles.

[0025] 2. Take 200 mg of SPEEK (sulfonation degree 62%), add 3mL N,N-dimethylformamide, dissolve to form SPEEK solution, add 1 wt% MOF-SO to the above polymer solution 3 H@GO, and ultrasonic 3h to make it evenly dispersed; the dispersion w...

Embodiment 2

[0028] 1. Ultrasonic dispersion of 150 mg GO in 45 mL of N,N-dimethylacetamide (DMA), then weighed 1000 mg of zirconium oxychloride octahydrate and 830 mg of sodium 2-sulfonic acid terephthalate were added to the above dispersion , then add 11.7mL of formic acid, and ultrasonically disperse. Transfer it to a 100 mL polytetrafluoroethylene liner, cover the lid and put it into the reactor to seal it tightly, then place it in a constant temperature oven at 150 °C for 24 h, and separate the reaction product by centrifugation. Wash continuously with fresh DMF solvent, and then with fresh CH 3 OH was washed several times, and the centrifuged product was finally placed in an oven at 50 °C for 6 hours to obtain MOF-SO 3 H@GO composite particles.

[0029] 2. Take 200 mg of SPEEK (sulfonation degree 62%), add 3mL N,N-dimethylformamide, dissolve to form SPEEK solution, add 2 wt% MOF-SO to the above polymer solution 3 H@GO, and ultrasonic 3h to make it evenly dispersed; the dispersion ...

Embodiment 3

[0031] 1. Ultrasonic dispersion of 150 mg GO in 45 mL of N,N-dimethylacetamide (DMA), then weighed 1000 mg of zirconium oxychloride octahydrate and 830 mg of sodium 2-sulfonic acid terephthalate were added to the above dispersion , then add 11.7mL of formic acid, and ultrasonically disperse. Transfer it to a 100 mL polytetrafluoroethylene liner, cover the lid and put it into the reactor to seal it tightly, then place it in a constant temperature oven at 150 °C for 24 h, and separate the reaction product by centrifugation. Wash continuously with fresh DMF solvent, and then with fresh CH 3 OH was washed several times, and the centrifuged product was finally placed in an oven at 50 °C for 6 hours to obtain MOF-SO 3 H@GO composite particles.

[0032] 2. Take 200 mg of SPEEK (sulfonation degree 62%), add 3mL N,N-dimethylformamide, dissolve to form SPEEK solution, add 3 wt% MOF-SO to the above polymer solution 3 H@GO, and ultrasonic 3h to make it evenly dispersed; the dispersion ...

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Abstract

The invention belongs to the technical field of membranes, and in particular relates to a sulfonate functionalized metal-organic framework and graphene oxide compound modified polymer hybrid proton exchange membrane and a preparation method thereof. According to the invention, a compound(MOF-SO3H@GO) of the sulfonate functionalized metal-organic framework(MOF-SO3H) and graphene oxide(GO) is prepared first and then doped into a polymer to obtain the sulfonate functionalized metal-organic framework and graphene oxide compound particles hybridized polymer hybrid proton exchange membrane. The proton exchange membrane has excellent proton conductivity under a high dampness condition, and simultaneously improves the fuel obstructive capability of the hybrid proton exchange membrane. Therefore, the (MOF-SO3H@GO) modified polymer hybrid proton exchange membrane has more superior selectivity. The method has a simple operational process, mild preparation conditions, relatively low production cost, convenience for batch and large-scale production, good industrial production basis and wide application prospects.

Description

technical field [0001] The invention belongs to the field of membrane technology, and in particular relates to a polymer hybrid proton exchange membrane synergistically modified by sulfonate-functionalized metal-organic framework-graphene oxide composite particles and a preparation method thereof. Background technique [0002] With the advantages of high efficiency and no pollution, fuel cells are gradually showing great promise as one of the most effective power sources to replace internal combustion engines. Among them, the sixth-generation fuel cell, namely direct methanol fuel cell, has outstanding advantages such as mild operating conditions, high energy density, no fuel pretreatment device and long service life. Therefore, it has gained wide attention from multiple aspects such as industry and academia. The proton exchange membrane is one of its core components. On the one hand, it provides a channel for the migration and transfer of protons, and on the other hand, it...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08J5/22C08K3/16C08K5/42C08K9/12C08L61/16H01M8/1025H01M8/0221
CPCC08J5/2256C08K3/16C08K5/42C08K9/12C08L2203/16C08L2203/20H01M8/1025C08L61/16Y02E60/50Y02P70/50
Inventor 孙华圳汤蓓蓓武培怡
Owner FUDAN UNIV
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