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Porphyrin-based metal-organic framework nanosphere as well as preparation method and application thereof

An organic framework and metal-based technology, applied in the field of porphyrin-based metal-organic framework nanospheres and its preparation, to achieve enhanced light conversion efficiency, simple operation, and improved yield

Pending Publication Date: 2022-02-22
SUZHOU INST OF NANO TECH & NANO BIONICS CHINESE ACEDEMY OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although metal-organic framework materials have been prepared and studied in large quantities, there are still few metal-organic framework microsheets with a size of 1-20 μm in the form of gauze, and further studies have made this gauze-like metal-organic framework with a size of 1-20 μm Condensation of organic framework sheets into nanospheres with coexistence of micropores and mesoporous pores has not yet been mentioned

Method used

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  • Porphyrin-based metal-organic framework nanosphere as well as preparation method and application thereof
  • Porphyrin-based metal-organic framework nanosphere as well as preparation method and application thereof
  • Porphyrin-based metal-organic framework nanosphere as well as preparation method and application thereof

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preparation example Construction

[0019] One aspect of the embodiments of the present invention provides a method for preparing porphyrin-based metal-organic framework nanospheres, which includes:

[0020] react a mixed reaction system containing mes-tetrakis(4-carboxyphenyl)porphine and / or metalloporphine, metal ions, promoters, organic solvents and water at 50-130°C for 1-5h to obtain a two-dimensional metal- Organic framework microsheets;

[0021] And, adding polyethylenimine to the mixed reaction system and performing a condensation reaction at 10-60° C. for 2-10 hours to obtain porphyrin-based metal-organic framework nanospheres.

[0022] In some more specific embodiments, the metalloporphines include mid-tetrakis(4-carboxyphenyl) iron porphine, mid-tetrakis(4-carboxyphenyl) copper porphine, mid-tetrakis(4-carboxyphenyl) Any one or a combination of two or more of phenyl) zinc porphine, medium-tetrakis(4-carboxyphenyl) cobalt porphine, medium-tetrakis(4-carboxyphenyl) manganese porphine, and not limited t...

Embodiment 1

[0048] The medium-tetrakis(4-carboxyphenyl)porphin used in this example was purchased from Tokyo Chemical Industry Co., Ltd. Reagent Company; copper nitrate and N,N-dimethylformamide were purchased from Sinopharm Group.

[0049] Prepare 1.0mmol / L meso-tetrakis(4-carboxyphenyl)porphin solution with N,N-dimethylformamide as solvent, and then prepare 10.0mmol / L copper nitrate solution with water as solvent. Add 2mL of tetrakis(4-carboxyphenyl)porphine solution and 1mL copper nitrate solution into the bottom flask, then add 10mL N,N-dimethylformamide, add 0.05g of benzoic acid, stir well, mix well The solution was heated in an oil bath with stirring at a temperature of 90° C. for a reaction time of 4 hours. After the reaction was completed, it was cooled to room temperature. Subsequently, 1 mL of polyethyleneimine with a concentration of 1000 mg / L and a molecular weight of 600 g / mol was added, and condensed at room temperature for 5 h under stirring to obtain porphyrin-based metal...

Embodiment 2

[0051] In this example, N,N-dimethylformamide is used as a solvent to prepare a 0.1mmol / L medium-tetrakis(4-carboxyphenyl)porphine solution, and then water is used as a solvent to prepare a 0.1mmol / L copper chloride solution . In a 100mL round-bottomed flask, add 2mL of tetrakis(4-carboxyphenyl)porphine solution and 1mL of copper chloride solution, then add 10mL of N,N-dimethylformamide, add 0.05g of benzoic acid, and stir well . The homogeneously mixed solution was heated and reacted in an oil bath with stirring at a temperature of 50° C. and a reaction time of 5 hours. After the reaction was completed, it was cooled to room temperature. Subsequently, 1 mL of polyethyleneimine with a concentration of 1000 mg / L and a molecular weight of 600 g / mol was added, and condensed at 60 ° C for 2 h under stirring to obtain porphyrin-based metal-organic framework nanospheres with coexistence of micropores and mesoporous pores, with a diameter of 60 nm. about.

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Abstract

The invention discloses a porphyrin-based metal-organic framework nanosphere as well as a preparation method and application thereof. The preparation method comprises the following steps: subjecting a mixed reaction system containing meso-tetra(4-carboxyphenyl)porphine and / or metal porphin, metal ions, an accelerant, an organic solvent and water to reacting at 50-130 DEG C for 1-5 hours to obtain a two-dimensional metal-organic framework structure micron sheet; and adding polyethyleneimine into a mixed reaction system obtained in the previous step, and carrying out a condensation reaction at 10-60 DEG C for 2-10 hours to obtain the porphyrin-based metal-organic framework nanosphere. According to the preparation method, the gauze-shaped micron large-size sheets are obtained by adjusting a ratio of porphin to metal ions, and then the porphyrin-based metal-organic framework nanosphere which is uniform in size and has coexisting micropores and mesopores are prepared through further reaction; and meanwhile, the porphyrin-based metal-organic framework nanosphere prepared by the method has wide application prospects in the fields of gas storage and separation, fuel cell performance conversion, biomedical imaging, cancer treatment and the like.

Description

technical field [0001] The invention belongs to the technical field of metal-organic framework nanomaterials, and specifically relates to a porphyrin-based metal-organic framework nanosphere and its preparation method and application, in particular to a method of using polyethylenimine to condense gauze-like micro-sheets Constructed porphyrin-based metal-organic framework nanospheres with coexistence of micropores and mesoporous pores, its preparation method and application. Background technique [0002] The large specific surface area and ordered pore structure of metal-organic framework materials endow them with various applications in gas storage and separation, fuel cell performance conversion, biomedical imaging, and cancer treatment. Although metal-organic framework materials have been prepared and studied in large quantities, there are still few metal-organic framework microsheets with a size of 1-20 μm in the form of gauze, and further studies have made this gauze-li...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J13/14C08G83/00C08G81/00
CPCB01J13/14C08G83/008C08G81/00B01J13/025Y02E60/50
Inventor 裴仁军赵岳五王金娥
Owner SUZHOU INST OF NANO TECH & NANO BIONICS CHINESE ACEDEMY OF SCI
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