阅读说明：本技术 一种水分散性二硫化钼的制备方法 (Preparation method of water-dispersible molybdenum disulfide ) 是由 肖玉良 张宗勇 李德龙 于 2021-10-22 设计创作，主要内容包括：本发明属于纳米材料制备技术领域,具体涉及一种水分散性二硫化钼的制备方法。所述的水分散性二硫化钼以二硫化钼和硫酸软骨素为原料,以甲酰胺为溶剂,加热反应制得。本发明通过硫酸软骨素对二硫化钼的表面物理吸附进行改性,使所合成的材料更具有亲水性,在水中达到更好的分散性,从而使二硫化钼在医药方面得到更好的运用。本发明的制备方法简单,原料简单易得,方便推广使用。(The invention belongs to the technical field of nano material preparation, and particularly relates to a preparation method of water-dispersible molybdenum disulfide. The water-dispersible molybdenum disulfide is prepared by heating and reacting molybdenum disulfide and chondroitin sulfate serving as raw materials and formamide serving as a solvent. According to the invention, the chondroitin sulfate is used for modifying the surface physical adsorption of the molybdenum disulfide, so that the synthesized material has hydrophilicity and achieves better dispersibility in water, and the molybdenum disulfide is better applied in the aspect of medicine. The preparation method is simple, the raw materials are simple and easy to obtain, and the preparation method is convenient to popularize and use.)

1. A preparation method of water-dispersible nano molybdenum disulfide is characterized in that molybdenum disulfide and chondroitin sulfate are used as raw materials, formamide is used as a solvent, and heating reaction is carried out to obtain the water-dispersible nano molybdenum disulfide.

2. The preparation method of the water-dispersible nano molybdenum disulfide according to claim 1, characterized by comprising the following steps:

(1) under the condition of stirring at 70-80 ℃, molybdenum disulfide is dispersed in formamide to prepare a molybdenum disulfide formamide solution; dissolving chondroitin sulfate in formamide to prepare chondroitin sulfate formamide solution; dropwise adding a molybdenum disulfide formamide solution into a chondroitin sulfate solution, wherein the mass ratio of molybdenum disulfide to chondroitin sulfate is 1: 1-10, stirring and reacting;

(2) and after the reaction is finished, transferring the liquid into a 1000Da dialysis bag for dialysis, and freeze-drying after the dialysis is finished to obtain the water-dispersible nano molybdenum disulfide.

3. The preparation method of the water-dispersible nano molybdenum disulfide according to claim 2, wherein the chondroitin sulfate is selected from one or more of pig chondroitin sulfate, cow chondroitin sulfate, shark chondroitin sulfate, chicken chondroitin sulfate and duck chondroitin sulfate.

4. The preparation method of the water-dispersible nano molybdenum disulfide according to claim 2, wherein the concentration of the molybdenum disulfide formamide solution is 0.1-1.0 mg/ml.

5. The preparation method of the water-dispersible nano molybdenum disulfide according to claim 2, wherein the concentration of the chondroitin sulfate solution is 5-10 mg/ml.

6. The preparation method of the water-dispersible nano molybdenum disulfide according to claim 2, wherein the dropping time of the formamide solution of molybdenum disulfide is 1-5 min.

7. The preparation method of the water-dispersible nano molybdenum disulfide according to claim 1, characterized by comprising the following steps: the preparation method of the molybdenum disulfide comprises the following steps:

(1) adding ammonium paramolybdate powder and distilled water into a reaction vessel, adding strong ammonia water, stirring, and heating to 45-50 ℃ for dissolution; adding an ammonium sulfide aqueous solution into the solution, heating to 50-75 ℃, stirring for reaction, cooling to room temperature after the reaction is finished, standing for crystallization, performing suction filtration, washing with distilled water, washing with absolute ethyl alcohol, and drying to obtain needle-shaped crystals;

(2) and simultaneously placing the crystals and ethylene glycol into a flask, reacting at 165-175 ℃ for 3-4 h, standing, centrifuging, washing with water, absolute ethyl alcohol and acetone respectively, and airing to obtain a black substance molybdenum disulfide.

8. The preparation method of the water dispersible nano molybdenum disulfide according to claim 7, wherein the mass volume ratio of the ammonium paramolybdate to the strong ammonia water is 1g/1-2 ml; the volume ratio of the distilled water to the concentrated ammonia water is 3: 1.

9. The method for preparing water-dispersible nano molybdenum disulfide according to claim 7, wherein when ammonium sulfide aqueous solution is added for reaction, the molar ratio of S: mo is 4-6: 1.

10. the method of claim 7, wherein the sulfur content in the ammonium sulfide aqueous solution is 14% by mass.

Technical Field

The invention belongs to the technical field of nano material preparation, and particularly relates to a preparation method of water-dispersible molybdenum disulfide.

Background

Natural MoS₂Is the main component of molybdenite, is in lead gray powder, is non-toxic, has strong metallic luster, is generally insoluble in water, alkali, acid and organic solvent, and is commonly used for preparing molybdate or molybdenum oxide in industry. With the development of nanometer material science, the research of nanometer molybdenum disulfide has received extensive attention, but molybdenum disulfide's water dispersibility is poor, has hindered its application research to a certain extent. Chinese patent publication No. CN109762369B discloses a method for preparing water-based high-dispersibility nano molybdenum disulfide, which comprises mixing molybdenum source, sulfur source and sulfur-containing compound, adding into solution of organic solvent and deionized water, and reactingObtaining mercaptoethanol modified molybdenum disulfide; and then sequentially adding toluene and mercaptoethanol modified nano molybdenum disulfide, organic tin and diisocyanate into a container under the protection of nitrogen, uniformly mixing, dropwise adding polyethylene glycol, reacting under a heating condition to prepare the polyethylene glycol modified molybdenum disulfide, wherein the polyethylene glycol modified molybdenum disulfide has good water dispersibility, obvious precipitation is not found after standing for 10 days, but the organic tin, the toluene and the diisocyanate adopted in the reaction are harmful to organisms, and the organic tin is forbidden to be used by the REACH act of the European Union.

Disclosure of Invention

The invention aims to overcome the characteristic of poor water dispersibility of nano molybdenum disulfide and provides a preparation method of water dispersible nano molybdenum disulfide.

In order to realize the purpose of the invention, the invention adopts the following technical scheme:

the preparation method of the water-dispersible nano molybdenum disulfide provided by the invention is characterized in that molybdenum disulfide and chondroitin sulfate are used as raw materials, formamide is used as a solvent, and the water-dispersible nano molybdenum disulfide is prepared by heating reaction.

The method comprises the following specific steps:

(1-1) dispersing molybdenum disulfide in formamide under the condition of stirring at 70-80 ℃ to prepare a molybdenum disulfide formamide solution; dissolving chondroitin sulfate in formamide to prepare chondroitin sulfate formamide solution; dropwise adding a molybdenum disulfide formamide solution into a chondroitin sulfate solution, wherein the mass ratio of molybdenum disulfide to chondroitin sulfate is 1: 1-10, stirring and reacting;

(1-2) after the reaction is finished, transferring the liquid into a 1000Da dialysis bag for dialysis, and freeze-drying after the dialysis is finished to obtain the water-dispersible nano molybdenum disulfide.

The chondroitin sulfate is selected from any one or more of pig chondroitin sulfate, cattle chondroitin sulfate, shark chondroitin sulfate, chicken chondroitin sulfate and duck chondroitin sulfate.

The concentration of the molybdenum disulfide formamide solution is 0.1-1.0 mg/ml.

The concentration of the chondroitin sulfate solution is 5-10 mg/ml.

The dripping time of the formamide solution of the molybdenum disulfide is 1-5 min.

The preparation method of the molybdenum disulfide comprises the following steps:

(2-1) adding ammonium paramolybdate powder and distilled water into a reaction vessel, adding strong ammonia water, stirring, and heating to 45-50 ℃ for dissolution; adding an ammonium sulfide aqueous solution into the solution, heating to 50-75 ℃, stirring for reaction, cooling to room temperature after the reaction is finished, standing for crystallization, performing suction filtration, washing with distilled water, washing with absolute ethyl alcohol, and drying to obtain needle-shaped crystals;

(2-2) putting the crystals and ethylene glycol into a flask at the same time, reacting at 165-175 ℃ for 3-4 h, standing, centrifuging, washing with water, absolute ethyl alcohol and acetone respectively, and airing to obtain a black substance molybdenum disulfide.

The mass volume ratio of the ammonium paramolybdate to the strong ammonia water is 1g/1-2 ml; the volume ratio of the distilled water to the concentrated ammonia water is 3: 1.

When an aqueous ammonium sulfide solution is added for reaction, the molar ratio of S: mo is 4-6: 1.

the mass fraction of the ammonium sulfide aqueous solution is 14%.

Compared with the prior art, the invention has the following beneficial effects: chondroitin sulfate is a polysaccharide biomacromolecule, has good water solubility, contains rich hydroxyl and carboxyl, can be adsorbed on the surface of the nano molybdenum disulfide through the hydroxyl and the carboxyl, further increases the water dispersibility of the molybdenum disulfide, and has simple and feasible production process. In addition, the chondroitin sulfate has good biocompatibility and low toxicity, and can reduce the biological toxicity of the molybdenum disulfide to a certain extent. According to the invention, the surface physical adsorption of molybdenum disulfide is modified, so that the synthesized material has hydrophilicity and achieves better dispersibility in water, and thus the molybdenum disulfide is better applied in the aspect of medicine. The preparation method is simple, the raw materials are simple and easy to obtain, and the preparation method is convenient to popularize and use.

Drawings

FIG. 1 shows MoS at different times₂And CS-MoS₂Water dispersion performance diagram, MoS on left₂Right side is CS-MoS₂；

FIG. 2 shows MoS₂And CS-MoS₂Transmission electron micrograph (D).

Detailed Description

The present invention will be further described with reference to the accompanying drawings and examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the invention.

Example 1

(1) A three-necked flask equipped with a reflux condenser and a thermometer was placed in a water bath, and 2.5g of ammonium paramolybdate powder was weighed into the three-necked flask, and 7.5ml of distilled water and 2.5ml of ammonia water were added thereto, stirred, and heated to 45 ℃ to be dissolved. To this solution was added, with stirring, an ammonium sulfide solution with a sulfur content of 14%, such that S: mo (molar ratio) ═ 4: 1, heating to 65 ℃, stirring and reacting for 1h to obtain dark red liquid after the reaction is finished, cooling the reactant to room temperature, and standing for crystallization. Filtering the liquid containing the crystal with a Buchner funnel, washing with cold distilled water for three times, washing the crystal with absolute ethyl alcohol for three times, pumping out the solvent, and drying in a vacuum drying oven to obtain dark red needle-shaped crystals;

(2) putting 0.065g of the red crystal and 30ml of glycol into a 100ml flask at the same time, then heating by using a constant-temperature electric heating jacket, reacting at 170 ℃ for 3 hours, standing, centrifuging and washing, washing 2 times by using 10ml of water, 3 times by using 10ml of absolute ethyl alcohol, 3 times by using 5ml of acetone, centrifuging for 5min at 10000r/min, and airing at room temperature to obtain a black substance molybdenum disulfide;

(3) under the condition of stirring at 70 ℃, molybdenum disulfide is dispersed in formamide to prepare a molybdenum disulfide formamide solution of 1.0 mg/ml; dissolving shark chondroitin sulfate in formamide to prepare 10mg/ml shark chondroitin sulfate formamide solution; dropwise adding a molybdenum disulfide formamide solution into a shark chondroitin sulfate formamide solution, wherein the mass ratio of molybdenum disulfide to shark chondroitin sulfate is 1: 10, the dropping time is 5 min.

(4) After the reaction is finished, transferring the liquid into a 1000Da dialysis bag, dialyzing with ultrapure water for 3 days, changing water once for 2h, and freeze-drying to obtain CS-MoS₂。

Example 2

(1) A three-neck flask provided with a reflux condenser and a thermometer is placed in a water bath, 2g of ammonium paramolybdate powder is weighed and placed in the three-neck flask, 9ml of distilled water is added, 3ml of ammonia water is added, and the mixture is stirred and heated to 45 ℃ for dissolution. To this solution was added, with stirring, an ammonium sulfide solution with a sulfur content of 14%, such that S: mo (molar ratio) ═ 5: 1, heating to 55 ℃, stirring and reacting for 1.5h to obtain dark red liquid after the reaction is finished, cooling the reactant to room temperature, and standing for crystallization. Filtering the liquid containing the crystal with a Buchner funnel, washing with cold distilled water for three times, washing the crystal with absolute ethyl alcohol for three times, pumping out the solvent, and drying in a vacuum drying oven to obtain dark red needle-shaped crystals;

(2) simultaneously placing 0.065g of the red crystal and 40ml of glycol into a 100ml flask, then heating by using a constant-temperature electric heating jacket, reacting at 165 ℃ for 4 hours, standing, centrifuging and washing, respectively washing with 10ml of water for 2 times, 5ml of absolute ethyl alcohol for 2 times, 2ml of acetone for 3 times, centrifuging at 10000r/min for 5min, and airing at room temperature to obtain a black substance molybdenum disulfide;

(3) under the condition of stirring at the temperature of 80 ℃, molybdenum disulfide is dispersed in formamide to prepare a molybdenum disulfide formamide solution with the concentration of 0.5 mg/ml; dissolving pig chondroitin sulfate in formamide to prepare 5mg/ml pig chondroitin sulfate formamide solution; dropwise adding a molybdenum disulfide formamide solution into a pig chondroitin sulfate formamide solution to ensure that the mass ratio of molybdenum disulfide to pig chondroitin sulfate is 1: 1, the dropping time is 5 min.

(4) After the reaction is finished, transferring the liquid into a 1000Da dialysis bag, dialyzing with ultrapure water for 3 days, changing water once for 2h, and freeze-drying to obtain CS-MoS₂。

Example 3

(1) A three-necked flask equipped with a reflux condenser and a thermometer was placed in a water bath, and 2.5g of ammonium paramolybdate powder was weighed into the three-necked flask, and 15ml of distilled water and 5ml of ammonia water were added thereto, stirred, and heated to 50 ℃ to be dissolved. To this solution was added, with stirring, an ammonium sulfide solution with a sulfur content of 14%, such that S: mo (molar ratio) ═ 6: 1, heating to 75 ℃, stirring and reacting for 1h to obtain dark red liquid after the reaction is finished, cooling the reactant to room temperature, and standing for crystallization. Filtering the liquid containing the crystal with a Buchner funnel, washing with cold distilled water for three times, washing the crystal with absolute ethyl alcohol for three times, pumping out the solvent, and drying in a vacuum drying oven to obtain dark red needle-shaped crystals;

(2) putting 0.065g of the red crystal and 25ml of glycol into a 100ml flask at the same time, then heating by using a constant-temperature electric heating jacket, reacting at 170 ℃ for 3 hours, standing, centrifuging and washing, washing 3 times by using 5ml of water, washing 2 times by using 10ml of absolute ethyl alcohol, washing 2 times by using 5ml of acetone, centrifuging for 5min at 10000r/min, and airing at room temperature to obtain a black substance molybdenum disulfide;

(3) under the condition of stirring at 75 ℃, molybdenum disulfide is dispersed in formamide to prepare a molybdenum disulfide formamide solution with the concentration of 0.1 mg/ml; dissolving bovine chondroitin sulfate in formamide to prepare a 5mg/ml bovine chondroitin sulfate formamide solution; dropwise adding a molybdenum disulfide formamide solution into a bovine chondroitin sulfate formamide solution to ensure that the mass ratio of molybdenum disulfide to bovine chondroitin sulfate is 1: 5, the dropping time is 5 min.

(4) After the reaction is finished, transferring the liquid into a 1000Da dialysis bag, dialyzing with ultrapure water for 1 day, changing water for 2 hours, and freeze-drying to obtain CS-MoS₂。