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Sulfonic acid functionalized zirconium-based metal organic framework material and preparation method and application thereof

A metal-organic framework, sulfonic acid functionalization technology, applied in chemical instruments and methods, chemical/physical processes, cation exchange, etc., can solve problems affecting proton conductivity, low density of thiophenols, etc.

Active Publication Date: 2019-01-25
GUANGDONG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, we found that the thiophenol in the ligand used is easily oxidized to thioquinone, which is not conducive to oxidation to the corresponding sulfonic acid, and the density of thiophenol in the channel is not high, resulting in a lower density of sulfonic acid groups in the framework, directly Affect the proton conduction performance

Method used

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  • Sulfonic acid functionalized zirconium-based metal organic framework material and preparation method and application thereof
  • Sulfonic acid functionalized zirconium-based metal organic framework material and preparation method and application thereof
  • Sulfonic acid functionalized zirconium-based metal organic framework material and preparation method and application thereof

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preparation example Construction

[0038] The present invention provides a method for preparing a sulfonic acid functionalized zirconium-based metal-organic framework material described in the above technical solution, comprising the following steps:

[0039] Mix 2,2'-dimercaptomethylene-4,4'-biphenyldicarboxylic acid, zirconium tetrachloride, acid compound and N,N-dimethylformamide and react to obtain the reaction product UiO-67 -2CH 2 SH;

[0040] Disperse the reaction product in hydrogen peroxide solution, oxidize, stir, acidify, centrifuge and wash to obtain the metal-organic framework material UiO-67-2CH 2 SO 3 H.

[0041] The preparation method provided by the invention uses mercapto functionalized polyvalent aromatic carboxylic acid as a ligand, utilizes post-synthesis method to oxidize mercapto to sulfonic acid group, and obtains a metal-organic framework material containing sulfonic acid group, so that it has higher proton conductivity. Metal-organic frameworks also have good thermal stability.

...

Embodiment 1

[0071] see figure 1 , figure 1 Synthesis of UiO-67-2CH for Example 1 of the present invention 2 SO 3 H's roadmap;

[0072] Synthetic steps of intermediate 1:

[0073] (1) Weigh 4-bromo-3-methylbenzoic acid methyl ester (1145.8mg, 5mmol), diboronic acid pinacol ester (635mg, 2.5mmol), potassium carbonate (2070mg, 15mmol), 1,1-bis (Diphenylphosphine) ferric palladium dichloride (366mg, 0.5mmol) was added into a 50mL two-necked reaction eggplant bottle (with a magnetic stirrer), vacuum pumping and nitrogen filling were repeated several times.

[0074] (2) Measure 15ml of dimethyl sulfoxide (DMSO) solvent into a 50ml single-necked flask, blow nitrogen for 10min, transfer the solvent to the two-necked reaction eggplant bottle through a vacuum tube under the protection of nitrogen gas, start stirring and place the two-necked reaction eggplant bottle in 85 ℃ oil bath reflux reaction for 8h.

[0075] (3) After the reaction is over, add a large amount of distilled water, extract ...

Embodiment 2

[0095] Synthetic steps of intermediate 1:

[0096] (1) Weigh 4-bromo-3-methylbenzoate (1100mg, 4.8mmol), biboronic acid pinacol ester (670.6mg, 2.64mmol), potassium carbonate (1656mg, 12mmol), 1,1- Add bis(diphenylphosphine)ironium dichloride palladium (350mg, 0.48mmol) into a 50mL two-necked reaction eggplant bottle (with a magnetic stirrer), vacuumize and fill with nitrogen several times.

[0097] (2) Measure 12ml of dimethyl sulfoxide (DMSO) solvent into a 50ml single-necked flask, blow nitrogen for 10mins, transfer the solvent to the two-necked reaction eggplant bottle through a vacuum tube under the protection of nitrogen gas, start stirring and place the two-necked reaction eggplant bottle in 85 ℃ oil bath reflux reaction for 7h.

[0098] (3) After the reaction is over, add a large amount of distilled water, extract with ethyl acetate, separate and purify the organic phase by silica gel chromatography (the eluent is a mixed solvent of petroleum ether and ethyl acetate in ...

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Abstract

The invention provides a sulfonic acid functionalized zirconium-based metal organic framework material and a preparation method and application thereof. The chemical formula of the metal organic framework material is Zr6O4(OH)4(C16H12O10S2)6. An aromatic carboxylic acid organic ligand containing sulfonic acid functional groups in the metal organic matrix material makes the metal organic frameworkmaterial have higher proton conductivity and better thermal stability. The preparation method comprises the steps that 2,2'-dimercaptopyl-4,4'-dicarboxylic acid is utilized as a sulfhydryl functionalized aromatic carboxylic acid ligand, the sulfhydryl groups are oxidized into sulfonic acid groups by utilizing a post-synthesis oxidation method, and a polysulfonic acid group functionalized zirconium-based metal organic framework material is obtained. Under the temperature of 80 DEG C and the relative humidity of 70% or below, the proton conductivity of the material is 1.11 * 10<-5> to 1.48 * 10<-5>S cm<-1>; and thermal analysis and varying temperature XRD indicate that the material shows obvious weightlessness and structure collapse at 450 DEG C or above and can keep structural stability at200 DEG C or below.

Description

technical field [0001] The invention belongs to the technical field of metal organic framework materials, and in particular relates to a sulfonic acid functionalized zirconium-based metal organic framework material, a preparation method and application thereof. Background technique [0002] Metal-Organic Frameworks (Metal-Organic Frameworks), also known as coordination polymers, are a class of periodic polymers formed by interconnecting inorganic metal centers (metal ions or metal clusters) and bridging organic ligands through self-assembly. A crystalline porous material with a network structure. It is different from traditional inorganic porous compounds and organic compounds, but it has the characteristics of both inorganic and organic compounds, and exhibits the advantages of high porosity, adjustable pore channels, and structural diversity, making it suitable for gas storage, adsorption and separation, and catalytic and other fields have broad application prospects. Re...

Claims

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Application Information

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IPC IPC(8): C08G83/00B01J39/17
CPCB01J39/17C08G83/008
Inventor 黄一涛何军陈思远王雷
Owner GUANGDONG UNIV OF TECH
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