CN112608732A - Preparation method of quantum dot/zeolite imidazole metal organic framework composite material - Google Patents
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Abstract
Description
Technical Field
The invention relates to a preparation method of a quantum dot/zeolite imidazole Metal Organic Framework (MOFs) composite material. In particular to a method for in-situ growth of quantum dots in zeolite imidazole metal organic framework materials. The invention belongs to the field of nano materials and novel quantum dots.
Background
Quantum Dots (QDs) are novel fluorescent nano materials, have the advantages of broadband absorption and narrow-band emission, adjustable emission wavelength along with particle size, large two-photon absorption cross section, long fluorescence service life, high fluorescence intensity and other excellent photochemical properties, and are widely applied to the biomedical fields of cell and living body imaging, immunochromatography detection and the like in recent years. In particular, the method has great application prospect in the aspects of high-sensitivity and high-flux biological analysis and detection. However, quantum dots are small in size (2-10 nm), and are difficult to separate and purify after coupling with small biological molecules such as nucleic acids or proteins. Meanwhile, most of commercialized quantum dots are semiconductor quantum dots, are poor in water solubility and high in toxicity, and greatly limit the application of the quantum dots in aspects of biomedical diagnosis and the like.
In order to solve the problems, quantum dot composite materials are mainly prepared at present, the water solubility and the biocompatibility of quantum dots are improved, and the separation problem of the quantum dots can be improved due to the larger size. And Metal Organic Frameworks (MOFs) are a class of crystalline porous materials with a periodic network structure formed by connecting inorganic metal centers (metal ions or metal clusters) and organic ligands with each other through self-assembly. The MOFs material has the advantages of large specific surface area, good biocompatibility, stable chemical and physical properties and biodegradability. Wherein the zeolite imidazole metal organic framework (ZIFs) is a porous catalytic material formed by self-assembling metal and imidazole groups, and has a typical expanded tetrahedral structure, wherein the metal-imidazole-metal bond is about 145。. Due to the unique porous structure, modifiable characteristics and excellent thermal and chemical stability, ZIFs are used in gas separation, catalysis and electronic devicesApplications in biosensing and drug delivery are wide. Therefore, the quantum dots prepared by the aid of the ZIFs structure can effectively solve the problems of uneven synthesis, poor water solubility, high toxicity and the like of the quantum dots, and has great application value.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a quantum dot/zeolite imidazole Metal Organic Framework (MOFs) composite material.
The purpose of the invention is realized by the following scheme: a preparation method of quantum dot/zeolite imidazole metal organic framework composite material takes MOFs of metal organic framework structure of zeolite imidazole as a carrier, and the composite material of quantum dot grows in situ in the composite material, which comprises the following steps:
1) dissolving 0.5-1g MOFs in 20 mL of 0.1M ammonium chloride solution, stirring at room temperature for 2-4 hr to obtain precipitate, centrifuging, washing with ultrapure water, and dissolving the precipitate in 15 mL of ultrapure water to obtain water solution;
2) dissolving 0.5-1g of quantum dot precursor in 15 mL of ultrapure water to obtain a quantum dot aqueous solution;
3) mixing the two solutions of steps 1) and 2) thoroughly, stirring at room temperature for 2 hr; subsequently, the process of the present invention,
4) adding 10 mL of 50-100 mg/mL sodium sulfide solution, stirring at room temperature for 2 hr, centrifuging, collecting precipitate, fully cleaning with ethanol and ultrapure water, drying in vacuum, calcining at high temperature under the nitrogen condition overnight, dissolving the obtained precipitate in 10 mL of hydrochloric acid, stirring at room temperature overnight, and then thoroughly cleaning with ultrapure water to obtain the quantum dot zeolite imidazole metal organic framework composite material.
According to the invention, an aminated MOFs material is adopted, and furthermore, amino ions inside the MOFs are replaced by zinc ions, and then sodium sulfide is adopted for vulcanization and high-temperature calcination, so that the quantum dot zeolite imidazole metal organic framework composite material is prepared.
The BET specific surface area of the quantum dot zeolite imidazole metal organic framework composite material is 200 m2/g-800 m2/g。
The quantum dot size of the quantum dot zeolite imidazole metal organic framework composite material is 5-20 nm.
In the step 1), the size of the MOFs is 50-400 nm.
In the step 2), the quantum dot precursor is any one of zinc nitrate, zinc chloride, zinc sulfate and cadmium chloride.
In the step 4), the high-temperature calcination temperature is 500-700 ℃.
According to the method, the zeolite imidazole metal organic framework materials with different sizes are prepared by controlling reaction conditions, and the fluorescent quantum dots are grown in situ in the zeolite imidazole metal organic framework materials by controlling the conditions, so that the quantum dot zeolite imidazole metal organic framework composite material is obtained. The composite material has the characteristics of uniform size, stable fluorescence performance and good biocompatibility, and can meet the requirements of biological detection application.
The invention has the advantages that:
(1) the quantum dots are synthesized in situ in the metal organic framework in an ion exchange mode, and because the quantum dots are grown in the MOFs material aperture in a limited mode, the uniformity of the synthesized quantum dots is improved, and the stability of the quantum dots in an aqueous solution is also enhanced by the MOFs shell.
(2) The prepared composite material has the advantages of enhanced electronic conduction, stable fluorescence performance and good biocompatibility, and can meet the requirements of biological detection and imaging application.
Drawings
FIG. 1 is a TEM image of ZnS @ MOFs nanoparticles prepared in example 1.
Detailed Description
The technical solution of the present invention is further described below by specific examples. The following examples are further illustrative of the present invention and do not limit the scope of the present invention.
Example 1
A quantum dot/zeolite imidazole metal organic framework composite material takes MOFs (metal organic framework) of zeolite imidazole as a carrier, and the composite material of quantum dots grows in situ in the composite material, and is prepared by the following steps:
1) zinc nitrate hexahydrate and 2-methylimidazole are selected as ZIF-8 synthetic materials, 7.5 g of 2-methylimidazole is dissolved in 9 mL of aqueous solution, and the mixture is uniformly stirred at the temperature of 37 ℃; 1 mL of zinc nitrate hexahydrate (125 mg) solution was added to the above solution, and the mixture was reacted at 37 ℃ for 30min with a stirring speed of 400 rpm/min; after the reaction is finished, centrifuging at 5000 rpm/min for 30min, separating and removing supernatant, and washing for three times to obtain ZIF-8 nanoparticles (MOFs);
2) dissolving 0.5g MOFs in 20 mL of 0.1M ammonium chloride solution, stirring at room temperature for 4 hr to obtain precipitate, centrifuging, washing with ultrapure water, and dissolving the precipitate in 15 mL of ultrapure water to obtain water solution;
3) dissolving 1g of quantum dot precursor zinc nitrate in 15 mL of ultrapure water to obtain a quantum dot aqueous solution;
4) mixing the two solutions of steps 2) and 3), stirring at room temperature for 2 hr; subsequently, the process of the present invention,
4) adding 10 mL of sodium sulfide solution with the concentration of 100 mg/mL, stirring at room temperature for 2 hr, centrifuging, collecting precipitate, fully cleaning by using ethanol and ultrapure water, drying in vacuum, calcining at 600 ℃ under the condition of nitrogen overnight, dissolving the obtained precipitate in 10 mL of hydrochloric acid, stirring at room temperature overnight, and then completely cleaning by using ultrapure water to obtain the quantum dot zeolite imidazole metal organic framework composite material, which is recorded as ZnS @ MOFs nano-particles.
As can be seen from fig. 1, the size of the prepared composite nanoparticles is about 130 nm.
Example 2
A quantum dot/zeolite imidazole metal organic framework composite material is prepared by the following steps, which are similar to the steps in the example 1:
1) zinc nitrate hexahydrate and 2-methylimidazole are selected as ZIF-8 synthetic materials, 7.5 g of 2-methylimidazole is dissolved in 9 mL of aqueous solution, and the mixture is uniformly stirred at the temperature of 37 ℃; 1 mL of zinc nitrate hexahydrate (125 mg) solution was added to the above solution, and the mixture was reacted at 37 ℃ for 30min at a stirring speed of 400 rpm/min; after the reaction is finished, centrifuging at 5000 rpm/min for 30min, separating and removing supernatant, and washing for three times to obtain ZIF-8 nanoparticles (MOFs);
2) dissolving 0.75 MOFs in 20 mL of 0.1M ammonium chloride solution, stirring at room temperature for 3 hr, centrifuging, washing with ultrapure water, and dissolving the obtained precipitate in 15 mL of ultrapure water to obtain an aqueous solution;
3) dissolving 0.5g of zinc nitrate in 15 mL of ultrapure water to obtain a quantum dot water solution;
4) mixing the above solutions of steps 2) and 3), stirring at room temperature for 2 hr; subsequently, the process of the present invention,
5) 10 mL of 100 mg/mL sodium sulfide solution was added, and the mixture was stirred at room temperature for 2 hr. Centrifuging, collecting precipitate, fully cleaning with ethanol and ultrapure water, and vacuum drying. Calcining at 650 ℃ under nitrogen overnight. Dissolving the obtained precipitate in 10 mL of hydrochloric acid, stirring at room temperature overnight, and then thoroughly cleaning with ultrapure water to obtain the quantum dot zeolite imidazole metal organic framework composite material.
Example 3
A quantum dot/zeolite imidazole metal organic framework composite material is prepared by the following steps, which are similar to the steps in the example 1:
1) zinc nitrate hexahydrate and 2-methylimidazole are selected as ZIF-8 synthetic materials, 8 g of 2-methylimidazole is dissolved in 9 mL of aqueous solution, and the mixture is uniformly stirred at the temperature of 37 ℃; 1 mL of zinc nitrate hexahydrate (150 mg) solution was added to the above solution, and the mixture was reacted at 37 ℃ for 30min at a stirring speed of 400 rpm/min; after the reaction is finished, centrifuging at 5000 rpm/min for 30min, separating and removing supernatant, and washing for three times to obtain ZIF-8 nanoparticles (MOFs);
2) dissolving 1g MOFs in 20 mL0.1M ammonium chloride solution, stirring at room temperature for 2 hr, centrifuging, washing with ultrapure water, and dissolving the obtained precipitate in 15 mL ultrapure water to obtain water solution;
3) dissolving 0.5g of quantum dot precursor cadmium chloride in 15 mL of ultrapure water to obtain a quantum dot aqueous solution;
4) mixing the above two solutions of steps 2) and 3), stirring at room temperature for 2 hr; subsequently, the process of the present invention,
5) 10 mL of 100 mg/mL sodium sulfide solution was added, and the mixture was stirred at room temperature for 2 hr. Centrifuging, collecting precipitate, fully cleaning with ethanol and ultrapure water, and vacuum drying. Calcining at 650 ℃ under nitrogen overnight. Dissolving the obtained precipitate in 10 mL of hydrochloric acid, stirring at room temperature overnight, and then thoroughly cleaning with ultrapure water to obtain the quantum dot zeolite imidazole metal organic framework composite material.
Example 4
A quantum dot/zeolite imidazole metal organic framework composite material is prepared by the following steps, which are similar to the steps in the example 1:
1) zinc nitrate hexahydrate and 2-methylimidazole are selected as ZIF-8 synthetic materials, 5g of 2-methylimidazole is dissolved in 9 mL of aqueous solution, and the mixture is uniformly stirred at the temperature of 37 ℃; 1 mL of zinc nitrate hexahydrate (100 mg) solution was added to the above solution, and the mixture was reacted at 37 ℃ for 30min at a stirring speed of 400 rpm/min; after the reaction is finished, centrifuging at 5000 rpm/min for 30min, separating and removing supernatant, and washing for three times to obtain ZIF-8 nanoparticles (MOFs);
2) dissolving 0.5 MOFs in 20 mL of 0.1M ammonium chloride solution, stirring at room temperature for 4 hr, centrifuging, washing with ultrapure water, and dissolving the obtained precipitate in 15 mL of ultrapure water to obtain an aqueous solution;
3) dissolving 0.5g of precursor cadmium chloride in 15 mL of ultrapure water to obtain a quantum dot aqueous solution;
4) mixing the above solutions of steps 2) and 3), stirring at room temperature for 2 hr; subsequently, the process of the present invention,
5) 10 mL of 100 mg/mL sodium sulfide solution was added, and the mixture was stirred at room temperature for 2 hr. Centrifuging, collecting precipitate, fully cleaning with ethanol and ultrapure water, and vacuum drying. Calcining at 700 ℃ under nitrogen overnight. Dissolving the obtained precipitate in 10 mL of hydrochloric acid, stirring at room temperature overnight, and then thoroughly cleaning with ultrapure water to obtain the quantum dot zeolite imidazole metal organic framework composite material.
Claims (6)
1. A preparation method of quantum dot/zeolite imidazole metal organic framework composite material is characterized in that MOFs of metal organic framework structure of zeolite imidazole is used as a carrier, and the composite material of quantum dot grows in situ in the MOFs, and comprises the following steps:
1) dissolving 0.5-1g MOFs in 20 mL of 0.1M ammonium chloride solution, stirring at room temperature for 2-4 hr to obtain precipitate, centrifuging, washing with ultrapure water, and dissolving the precipitate in 15 mL of ultrapure water to obtain water solution;
2) dissolving 0.5-1g of quantum dot precursor in 15 mL of ultrapure water to obtain a quantum dot aqueous solution;
3) mixing the two solutions of steps 1) and 2) thoroughly, stirring at room temperature for 2 hr; subsequently, the process of the present invention,
4) adding 10 mL of 50-100 mg/mL sodium sulfide solution, stirring at room temperature for 2 hr, centrifuging, collecting precipitate, fully cleaning with ethanol and ultrapure water, drying in vacuum, calcining at high temperature under the nitrogen condition overnight, dissolving the obtained precipitate in 10 mL of hydrochloric acid, stirring at room temperature overnight, and then thoroughly cleaning with ultrapure water to obtain the quantum dot zeolite imidazole metal organic framework composite material.
2. The preparation method of the quantum dot/zeolite imidazole-based metal organic framework composite material according to claim 1, wherein the BET specific surface area of the quantum dot zeolite imidazole-based metal organic framework composite material is 200 m2/g-800 m2/g。
3. The preparation method of the quantum dot/zeolite imidazole-based metal organic framework composite material according to claim 1, wherein the quantum dot size of the quantum dot zeolite imidazole-based metal organic framework composite material is 5-20 nm.
4. The method for preparing the quantum dot/zeolite imidazole-based metal organic framework composite material according to claim 1, wherein in the step 1), the size of the MOFs is 50-400 nm.
5. The method for preparing the quantum dot/zeolite imidazole-based metal organic framework composite material according to claim 1, wherein in the step 2), the quantum dot precursor is any one of zinc nitrate, zinc chloride, zinc sulfate and cadmium chloride.
6. The method for preparing the quantum dot/zeolite imidazole-based metal organic framework composite material according to claim 1, wherein the high-temperature calcination temperature in the step 4) is 500-700 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107983272A (en)* | 2016-10-26 | 2018-05-04 | 中国科学院化学研究所 | Sulfide encapsulated particles and preparation method and application |
| CN109713267A (en)* | 2018-12-24 | 2019-05-03 | 肇庆市华师大光电产业研究院 | A kind of novel cathode material for lithium ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107983272A (en)* | 2016-10-26 | 2018-05-04 | 中国科学院化学研究所 | Sulfide encapsulated particles and preparation method and application |
| CN109713267A (en)* | 2018-12-24 | 2019-05-03 | 肇庆市华师大光电产业研究院 | A kind of novel cathode material for lithium ion battery and preparation method thereof |
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