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Method for degrading organic dye through metal organic framework film based on metalloporphyrin

A metal-organic framework, organic dye technology, applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, water pollutants, etc., to achieve the effect of convenient recycling and good catalytic effect

Active Publication Date: 2016-02-03
HUNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the synthesis of MOF films containing uncoordinated metalloporphyrins on the horizontal layer by the LbL method has not been reported.
However, there is no report on the photocatalytic degradation of dye wastewater using transparent metalloporphyrin MOF membranes with catalytic active sites.

Method used

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  • Method for degrading organic dye through metal organic framework film based on metalloporphyrin
  • Method for degrading organic dye through metal organic framework film based on metalloporphyrin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] The APTMS-treated glass substrates (2x3cm) were successively dissolved in zinc acetate (0.1mmol / L), 5,10,15,20-tetra-p-carboxyphenylmanganese porphyrin (2μmol / L) and 2,2'-bis Soak in an ethanol solution of methyl-4,4'-bipyridine (2 μmol / L) at 40°C for 10-12 minutes, wash with ethanol before each soaking, one cycle of soaking is a growth cycle, and 7 cycles of soaking to get a growth cycle A 7-layer MnPor-MOF film was fabricated. Place it in a mesh support and suspend it in methylene blue aqueous solution (4×10 -5 mol / L, 50ml), and placed in the dark for 30 minutes to make the catalyst reach adsorption-desorption equilibrium in the reaction liquid. Then irradiate the glass substrate with 300W xenon arc lamp, H 2 o 2 and methylene blue catalytic photolysis system. The change of absorbance of methylene blue at 665nm at different irradiation times was measured by UV-vis spectrometer to indicate the degree of degradation of methylene blue. After 180min of reaction, the d...

Embodiment 2

[0015] The APTMS-treated glass substrates (2x3cm) were respectively dissolved in zinc acetate (0.1mmol / L), 5,10,15,20-tetracarboxyphenylcobalt porphyrin (2μmol / L) and 2,2'-bis Soak in an ethanol solution of methyl-4,4'-bipyridine (2 μmol / L) at 40°C for 10-12 minutes, wash with ethanol before each soak, and soak for 14 cycles to obtain a CoPor-MOF film with 14 layers grown . Place it in an aqueous solution of Rhodamine B (4×10 -5 mol / L, 50ml), then use a 300W xenon arc lamp to irradiate the glass substrate, H 2 o 2 and rhodamine B catalytic photolysis system. The degree of degradation was expressed by measuring the change of absorbance at 554nm by UV-vis spectrometer, and the degradation rate of rhodamine exceeded 95% after 120 minutes of reaction.

Embodiment 3

[0017] The APTMS-treated glass substrates (2x3cm) were successively dissolved in zinc acetate (0.1mmol / L), 5,10,15,20-tetra-p-carboxyphenylmanganese porphyrin (2μmol / L) and 2,2'-bis Soak in an ethanol solution of methyl-4,4'-bipyridine (2 μmol / L) at 40°C for 10-12 minutes, wash with ethanol before each soaking, one cycle of soaking is a growth cycle, and 14 cycles of soaking to get a growth cycle A 14-layer MnPor-MOF film was fabricated. Place it in methylene blue (1×10 -5 mol / L), Rhodamine B (1×10 -5 mol / L), methyl orange (2×10 -5 mol / L) mixture solution (50mL), then irradiate the catalytic system with a 300W xenon arc lamp, and measure the change of absorbance at 665nm, 554nm and 464nm by UV–vis spectrometer to indicate the degree of degradation, and the degradation rate after 120min of reaction 96%, 95%, 97%, respectively.

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Abstract

The invention discloses a method for degrading organic dye through a metal organic framework film based on metalloporphyrin. The method is characterized in that the porphyrin metal organic framework film is generated on the surface of a transparent glass sheet and placed on a net-shaped support to be hung in an organic dye solution, and irradiation is performed for 1-4 h with the visible light intensity of 300 W at indoor temperature so that the organic dye solution can be degraded to the concentration at which the organic dye solution can be discharged. The preparation process of the metal organic framework film based on metalloporphyrin is characterized in that the transparent glass sheet pretreated with 3-APTMS is reacted with (4-carboxyphenyl)manganese(iron / cobalt)porphyrin, a solution containing Zn2+ and 2,2'-dimethyl-4,4'-bipyridine in a steeping mode, a product is washed with solvent after one time of steeping circulation is completed, the steeping step is repeated, and the thickness of the film is controlled by the number of steeping circulation times, so that the oriented, ordered and porous porphyrin metal organic framework film is prepared. According to the method, the metal organic framework film is used for performing light degradation on a single or mixed solution formed by methylene blue, methyl orange and rhodamine, is good in catalytic effect and convenient to recycle, and is a replaceable good novel material used for degrading organic dye.

Description

technical field [0001] The invention relates to a method for degrading organic dye wastewater by a metal-organic framework membrane material based on a metalloporphyrin-based metal-organic framework membrane material with orderly orientation and controllable membrane thickness. Background technique [0002] Metal-organic frameworks (MOFs for short), as a new type of porous inorganic-organic hybrid crystalline materials, have attracted extensive attention in the fields of chemistry, materials, and physics. MOFs, also known as coordination polymers, are a kind of network framework crystals that use metal ions or metal ion clusters as nodes and self-assemble with carboxylic acid or nitrogen-containing organic ligands through coordination bonds to form a periodic arrangement. state material. Combining the characteristics of inorganic and organic materials, MOFs have the advantages of diverse composition and structure, large specific surface area, pore size, and adjustable surfa...

Claims

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Application Information

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IPC IPC(8): B01J31/22C02F1/30C02F101/30
Inventor 阳卫军周元蓉朱军辉谭志伟
Owner HUNAN UNIV
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