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Preparation and application of nanometer composite material based on porphyrin metal organic framework and ternary sulfide

A metal-organic framework, nanocomposite technology, applied in organic compound/hydride/coordination complex catalysts, chemical/physical processes, water pollutants, etc., can solve problems such as limiting the types of dye adsorption

Inactive Publication Date: 2019-03-15
NORTHWEST NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Generally, MOFs are either positively charged or negatively charged overall, which limits the types of dyes adsorbed
However, the porphyrin MOFs material PCN-224 can adsorb both cationic dyes and anionic dyes, which provides the necessary conditions for the adsorption of anionic and cationic dyes, which cannot be achieved by general MOFs materials.

Method used

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  • Preparation and application of nanometer composite material based on porphyrin metal organic framework and ternary sulfide
  • Preparation and application of nanometer composite material based on porphyrin metal organic framework and ternary sulfide
  • Preparation and application of nanometer composite material based on porphyrin metal organic framework and ternary sulfide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Embodiment 1, ZnIn 2 S 4 Preparation and performance research of @PCN-224(10%)

[0039] (1) Preparation of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (TCPP): Take 3.04 g (20.25 mmol) of 4-formylbenzoic acid and 1.4 g (20.25 mmol) of redistilled pyrrole , added to 60 mL of propionic acid, heated to reflux for 2 to 3 hours; then the reaction mixture was cooled to room temperature, and 75 mL of methanol was added, while cooling and stirring in an ice bath for 0.5 to 1 hour; centrifuged to obtain a precipitate, washed with methanol and heated distilled water Several times until the filtrate is clear. Finally, the obtained purple powder was dried in an oven at 60-80°C for 10-12 hours to obtain 0.79 g TCPP.

[0040] (2) Preparation of PCN-224: take 50mg TCPP, 78mg zirconium tetrachloride (ZrCl 4 ), 2700mg of benzoic acid (BA), ultrasonically dissolved in 10mL N,N-dimethylformamide, then heat-treated at 100-140°C for 45-50 hours, cooled to room temperature, centrifuged ...

Embodiment 2

[0045] Example 2, ZnIn 2 S 4 Preparation and performance research of @PCN-224 (20%)

[0046] (1) Preparation of TCPP: Same as Example 1;

[0047] (2) Preparation of PCN-224: Same as Example 1;

[0048] (3) Activation of PCN-224: Same as Example 1;

[0049] (4) ZnIn 2 S 4 Preparation of @PCN-224 nanocomposite: Take 0.106g PCN-224 powder and disperse it into a mixed solution of 15 mL N,N-dimethylformamide and 5mL glycerol; take 0.136g ZnCl 2 , 0.586g InCl 3 4H 2 O, 0.301g TAA, was added to the mixed solution, and stirred at room temperature for 1.5 hours; the obtained suspension was transferred to a polytetrafluoroethylene lining, and kept at 180°C for 10 hours, cooled to room temperature, and the obtained The solid product was washed several times with distilled water and ethanol, centrifuged to separate the precipitate, and dried at 60~80°C to obtain a solid powder that is ZnIn 2 S 4 @PCN-224 composite material, where the mass percentage of PCN-224 is 20%, marked as ...

Embodiment 3

[0052] Embodiment 3, ZnIn 2 S 4 Preparation and performance research of @PCN-224 (30%)

[0053] (1) Preparation of TCPP: Same as Example 1;

[0054] (2) Preparation of PCN-224: Same as Example 1;

[0055] (3) Activation of PCN-224: Same as Example 1;

[0056] (4) ZnIn 2 S 4 Preparation of @PCN-224 nanocomposite material: Take 0.181g PCN-224 powder and disperse it into a mixed solution of 15mL N,N-dimethylformamide and 5mL glycerol; take 0.136g ZnCl 2 , 0.586g InCl 3 4H 2 O, 0.301g TAA, was added to the mixed solution and stirred at room temperature for 1.5 hours; the obtained suspension was transferred to a polytetrafluoroethylene lining, and kept at 200°C for 8 hours, cooled to room temperature, and the resulting solid The product was washed several times with distilled water and ethanol, centrifuged to separate the precipitate, and dried at 60~80°C to obtain a solid powder that is ZnIn 2 S 4 @PCN-224 composite material, where the mass percentage of PCN-224 is 30%, ...

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Abstract

The invention provides a nanometer composite material ZnIn2S4@PCN-224 based on ternary sulfide ZnIn2S4 and porphyrin MOFs (Metal-organic Frameworks). The nanometer composite material is prepared by the following steps: firstly dispersing activated PCN-224 into a N,N-dimethyl formamide-glycerol mixed solution, then adding ZnCl2, InCl3.4H2O and TAA and stirring for 0.5-1.5 hours; and performing heatinsulation treatment on a mixed suspension for 8-12 hours at a temperature of 160-200 DEG C, cooling to a room temperature, washing a solid product with distilled water and ethanol, performing centrifugal separation and precipitation, and drying to obtain solid powder, namely the ZnIn2S4@PCN-224. The nanometer composite material ZnIn2S4@PCN-224 provided by the invention has the benefits that theZnIn2S4 is loaded onto the porphyrin metal-organic framework PCN-224 through a solvo-thermal method, so that on one hand, organic pollutants can be better absorbed, and on the other hand, the separation efficiency of photo-generated electrons and holes is remarkably improved, and the photo-catalytic hydrogen production activity is significantly improved.

Description

technical field [0001] The invention relates to the preparation of a porphyrin-based metal-organic framework composite material, in particular to a ternary sulfide ZnIn 2 S 4 Nanocomposite ZnIn coupled with porphyrin MOFs 2 S 4 The method of @PCN-224, the invention also involves ZnIn 2 S 4 Performance of @PCN-224 nanocomposites for adsorption of organic pollutants and hydrogen production under visible light. Background technique [0002] In recent years, the problem of water pollution has become increasingly serious. Due to the characteristics of high chroma, high toxicity and refractory degradation, dye wastewater has a great impact on the environment and human health. Therefore, the treatment of dye wastewater has become a hot research topic at present. There are many treatment methods for dye wastewater, among which the physical adsorption method has become the most commonly used method for treating dyes due to its simple operation and high removal efficiency. Act...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J20/22B01J20/30C02F1/28B01J31/26C02F101/34C02F101/36C02F101/38
CPCB01J20/226C02F1/28C02F1/281C02F1/285B01J31/26C02F2101/34C02F2101/38C02F2101/40C02F2101/36B01J2531/025B01J2531/48B01J2531/0213B01J35/39
Inventor 王磊金鹏霞段树华姜曼卢华宝佘厚德黄静伟王其召
Owner NORTHWEST NORMAL UNIVERSITY
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