Preparation method and application of magnesium phosphate nanoparticles
Magnesium phosphate nanoparticles are prepared through injection dropping addition and gelatin wrapping technology, which solves the agglomeration problem caused by high-temperature calcination, realizes the stability of nano size and efficient preparation method, and enhances its application potential in the fields of catalysis and biomedical.
Patent Information
- Application Number
- CN202411893653.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-20
- Publication Date
- 2025-02-14
AI Technical Summary
The existing preparation methods of magnesium phosphate are prone to agglomeration of nanoparticles during high-temperature calcination, forming larger-sized sintered bodies, limiting their further application.
The injection dropwise addition method is used to mix water-soluble magnesium salt and phosphorus salt under high-speed stirring to form an amorphous magnesium phosphate precursor. It is then coated with gelatin and freeze-drying to avoid agglomeration caused by high-temperature calcination, and finally calcined at high temperature to form crystalline properties. High magnesium phosphate nanoparticles.
The high temperature sintering of nanomagnesium phosphate was successfully avoided, ensuring the nanoscale of the product, and improving its catalytic activity and biomedical application potential.
Smart Images
Figure CN119430109A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a method in the technical field of biomedical materials, in particular to a method for preparing nano-scale magnesium phosphate particles. Background Art
[0002] Magnesium phosphate (Mg3(PO4)2) has high biocompatibility, good degradation performance and excellent ionic conductivity, which makes it have great application potential in many fields such as biomedicine, environmental protection, energy storage and conversion. Nano-scale magnesium phosphate particles have high specific surface area and reactivity, and have unique advantages in some application scenarios. For example, in the application of magnesium phosphate bone cement, magnesium phosphate is used as the raw material of solid phase powder. Nano-magnesium phosphate enables it to dissolve quickly to form hydrogel during hydration, which helps to promote the continuous growth and aggregation growth of crystals of hydration products. The connection of gel will become more and more dense, and finally form a hardened structure, so that the hardened body of magnesium phosphate has high mechanical properties. In the field of catalysis, the size of nano-magnesium phosphate particles will affect its catalytic activity. Generally, the smaller the size, the larger the specific surface area and the higher the catalytic activity. Therefore, the size of the catalyst is usually required to be between 10 nanometers and 100 nanometers. In the field of environmental protection, the size of nano-magnesium phosphate particles used for water treatment and pollutant adsorption is usually required to be between 100 nanometers and 500 nanometers to provide sufficient adsorption sites and adsorption efficiency. At present, the commonly used methods for preparing magnesium phosphate include solution method, solid phase calcination method, hydrothermal synthesis method, etc. The commonly used solution method first forms an amorphous magnesium phosphate precursor through ion coprecipitation reaction in the solution, and then makes it crystalline through high temperature reaction. However, nanoparticles tend to agglomerate during high temperature calcination to form a larger sintered body, which limits its further application. Summary of the invention
[0003] The purpose of the present invention is to provide a preparation method and application of magnesium phosphate nanoparticles.
[0004] The objective of the present invention is achieved by the following technical scheme: a water-soluble magnesium salt and a water-soluble phosphorus salt are mixed by an injection drop method at a magnesium / phosphorus molar ratio of 3:2 under high-speed stirring to form an amorphous magnesium phosphate precursor; after the product is filtered, it is fully washed and precipitated with deionized water until the pH value of the filtrate is neutral, then the precipitate is dispersed with a gelatin solution, and freeze-dried; the dried powder is calcined at a high temperature to make it lose crystal water, so as to form magnesium phosphate nanoparticles with high crystallinity.
[0005] The present invention comprises the following steps: 1. Prepare a water-soluble magnesium salt solution with a concentration of 0.1-1 mol / L and a water-soluble phosphate salt solution with a concentration of 0.1-1 mol / L; the water-soluble magnesium salt includes one or more of magnesium chloride, magnesium nitrate, magnesium acetate, magnesium citrate, and magnesium gluconate; the water-soluble phosphate salt includes one or more of sodium hydrogen phosphate, potassium hydrogen phosphate, and ammonium hydrogen phosphate; 2. Use alkali solution to adjust the pH of the phosphate solution to 9-10, and under high-speed stirring, add the above magnesium salt solution to the above phosphate solution at 1-50mL / min, the total molar ratio of magnesium / phosphorus is 3:2, and alkali solution is continuously added during the reaction to maintain the pH value. The alkali solution includes one or more of ammonia water, sodium hydroxide, and potassium hydroxide; after the addition is completed, the reaction is continued for 2 hours, and then the mixed solution is filtered and the precipitate is fully washed with deionized water until the filtrate pH is neutral.
[0006] 3. Disperse the precipitate with 1-5% (w / v) gelatin solution and freeze-dry.
[0007] 4. The dried powder is calcined at 1150°C for 2-4 hours, and the product is mechanically crushed to obtain magnesium phosphate nanoparticles.
[0008] The advantages of the present invention are: 1. The present invention drips reactants under high-speed stirring to form a co-precipitated magnesium phosphate precursor, and then freeze-drying is used to obtain gelatin-coated precursor nanoparticles to avoid high-temperature sintering of nano-magnesium phosphate, and finally form nano-sized magnesium phosphate particles.
[0009] 2. The preparation method of the present invention is simple, the raw materials used are simple, suitable for mass production, and has broad clinical application prospects. BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Figure 1 This is a SEM image of the magnesium phosphate nanoparticles prepared in Example 1 of the present invention.
[0011] Figure 2 This is the XRD pattern of the magnesium phosphate precursor prepared in Example 1 of the present invention.
[0012] Figure 3 This is the XRD pattern of the magnesium phosphate nanoparticles prepared in Example 1 of the present invention.
[0013] Figure 4 This is a SEM image of the high-temperature sintered magnesium phosphate prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION
[0014] The following examples are implemented based on the technical solutions of the invention, and provide detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to the following examples.
[0015] Example 1 A magnesium phosphate nanoparticle is prepared according to the following steps: (1) Prepare a 1 mol / L water-soluble magnesium chloride solution and a 1 mol / L disodium hydrogen phosphate solution, and adjust the pH of the disodium hydrogen phosphate solution to 10 with sodium hydroxide; (2) Under high-speed stirring at 400 rpm, 3 L of the above magnesium chloride solution was added dropwise to 2 L of disodium hydrogen phosphate solution at a rate of 15 mL / min, and alkali solution was continuously added during the reaction to maintain the pH value; after the addition was completed, the reaction was continued for 2 h, and the mixed solution was filtered and the precipitate was fully washed with deionized water until the pH of the filtrate was neutral; (3) Disperse the precipitate with 1% (w / v) gelatin solution and freeze-dry. The XRD pattern of the magnesium phosphate precursor is shown in Figure 2 ; After drying, the powder was calcined at 1150°C for 4 hours; the product was mechanically crushed to obtain magnesium phosphate nanoparticles.
[0016] The SEM image of the obtained magnesium phosphate nanoparticles is shown in Figure 1 , XRD pattern see Figure 3 .
[0017] Example 2 A magnesium phosphate nanoparticle is prepared according to the following steps: (1) Prepare 0.5 mol / L magnesium nitrate solution and 0.5 mol / L diammonium hydrogen phosphate solution, and adjust the pH of the diammonium hydrogen phosphate solution to 10 with ammonia water; (2) Under mechanical stirring at 400 rpm, 3 L of the above magnesium nitrate solution was added dropwise to 2 L of diammonium hydrogen phosphate solution at a rate of 15 mL / min, and an aqueous ammonia solution was continuously added during the reaction to maintain the pH value; after the addition was completed, the reaction was continued for 2 h, and then the mixed solution was filtered and the precipitate was fully washed with deionized water until the pH of the filtrate was neutral; (3) The precipitate was dispersed with 1% (w / v) gelatin solution and freeze-dried. After drying, the powder was calcined at 1150°C for 4 h, and the product was mechanically crushed to obtain magnesium phosphate nanoparticles.
[0018] Example 3 A magnesium phosphate nanoparticle is prepared according to the following steps: (1) Prepare 1 mol / L magnesium chloride solution and 1 mol / L dipotassium hydrogen phosphate solution, and adjust the pH of the dipotassium hydrogen phosphate solution to 10 with potassium hydroxide; (2) Under mechanical stirring at 400 rpm, 3 L of the above magnesium chloride solution was added dropwise to 2 L of dipotassium hydrogen phosphate solution at a rate of 15 mL / min, and potassium hydroxide solution was continuously added during the reaction to maintain the pH value; after the addition was completed, the reaction was continued for 2 h, and then the mixed solution was filtered and the precipitate was fully washed with deionized water until the pH of the filtrate was neutral; (3) The precipitate was dispersed with 1% (w / v) gelatin solution and freeze-dried. After drying, the powder was calcined at 1150°C for 4 h, and the product was mechanically crushed to obtain magnesium phosphate nanoparticles.
[0019] Comparative Example 1 A magnesium phosphate nanoparticle, which is otherwise the same as Example 1 except that gelatin dispersion is not performed, is prepared according to the following steps: (1) Prepare 1 mol / L magnesium chloride solution and 1 mol / L disodium hydrogen phosphate solution, and adjust the pH of the disodium hydrogen phosphate solution to 10 with sodium hydroxide; (2) Under mechanical stirring at 400 rpm, 3 L of the above magnesium chloride solution was added dropwise to 2 L of disodium hydrogen phosphate solution at a rate of 15 mL / min, and NaOH solution was continuously added during the reaction to maintain the pH value; after the addition was completed, the reaction was continued for 2 h, and then the mixed solution was filtered and the precipitate was fully washed with deionized water until the pH of the filtrate was neutral; (3) The obtained precipitate with a neutral pH value is directly freeze-dried, and the powder is calcined at 1150° C. for 4 h after drying. The product is mechanically crushed to obtain magnesium phosphate nanoparticles.
[0020] The SEM image of the high temperature sintered magnesium phosphate prepared in this comparative example is shown in Figure 4 shown.
Claims
1. A method for preparing magnesium phosphate nanoparticles, characterized in that: The following steps are involved: (1) preparing a water-soluble magnesium salt solution with a concentration of 0.1-1 mol / L and a water-soluble phosphate salt solution with a concentration of 0.1-1 mol / L; the water-soluble magnesium salt includes one or more of magnesium chloride, magnesium nitrate, magnesium acetate, magnesium citrate, and magnesium gluconate; the water-soluble phosphate salt includes one or more of sodium hydrogen phosphate, potassium hydrogen phosphate, and ammonium hydrogen phosphate; (2) adjusting the pH value of the phosphate solution to 9-10 with an alkali solution, and adding the above-mentioned magnesium salt solution dropwise to the phosphate solution at a rate of 1-50 mL / min under high-speed stirring, wherein the total molar ratio of magnesium to phosphorus is 3:2, and continuously adding the alkali solution during the reaction to maintain the pH value; after the addition is completed, the reaction is continued for 2 hours, and the mixed solution is filtered by suction, and the precipitate is fully washed with deionized water until the pH value of the filtrate is neutral; (3) Dispersing the precipitate with 1-5% (w / v) gelatin solution and freeze-drying the mixture; calcining the dried powder at 1150°C for 2-4 hours, and mechanically crushing the product to obtain magnesium phosphate nanoparticles.
2. The method for preparing magnesium phosphate nanoparticles according to claim 1, characterized in that: The alkaline solution in step (2) includes one or more of ammonia water, sodium hydroxide and potassium hydroxide.
3. A method for preparing magnesium phosphate nanoparticles according to claim 1 or 2, characterized in that: Prepare as follows: (1) Prepare a 1 mol / L water-soluble magnesium chloride solution and a 1 mol / L disodium hydrogen phosphate solution, and adjust the pH of the disodium hydrogen phosphate solution to 10 with sodium hydroxide; (2) Under high-speed stirring at 400 rpm, 3 L of the above magnesium chloride solution was added dropwise to 2 L of disodium hydrogen phosphate solution at a rate of 15 mL / min, and alkali solution was continuously added during the reaction to maintain the pH value; after the addition was completed, the reaction was continued for 2 h, and the mixed solution was filtered and the precipitate was fully washed with deionized water until the pH of the filtrate was neutral; (3) The precipitate was dispersed with 1% (w / v) gelatin solution and freeze-dried. The XRD pattern of the magnesium phosphate precursor is shown in Figure 2. After drying, the powder was calcined at 1150°C for 4 hours. The product is mechanically crushed to obtain magnesium phosphate nanoparticles.
4. The method for preparing magnesium phosphate nanoparticles according to claim 1 or 2, characterized in that: Prepare as follows: (1) Prepare 0.5 mol / L magnesium nitrate solution and 0.5 mol / L diammonium hydrogen phosphate solution, and adjust the pH of the diammonium hydrogen phosphate solution to 10 with ammonia water; (2) Under mechanical stirring at 400 rpm, 3 L of the above magnesium nitrate solution was added dropwise to 2 L of diammonium hydrogen phosphate solution at a rate of 15 mL / min, and an aqueous ammonia solution was continuously added during the reaction to maintain the pH value; after the addition was completed, the reaction was continued for 2 h, and then the mixed solution was filtered and the precipitate was fully washed with deionized water until the pH of the filtrate was neutral; (3) The precipitate was dispersed with 1% (w / v) gelatin solution and freeze-dried. After drying, the powder was calcined at 1150°C for 4 h, and the product was mechanically crushed to obtain magnesium phosphate nanoparticles.
5. The method for preparing magnesium phosphate nanoparticles according to claim 1 or 2, characterized in that: Prepare as follows: (1) Prepare 1 mol / L magnesium chloride solution and 1 mol / L dipotassium hydrogen phosphate solution, and adjust the pH of the dipotassium hydrogen phosphate solution to 10 with potassium hydroxide; (2) Under mechanical stirring at 400 rpm, 3 L of the above magnesium chloride solution was added dropwise to 2 L of dipotassium hydrogen phosphate solution at a rate of 15 mL / min, and potassium hydroxide solution was continuously added during the reaction to maintain the pH value; after the addition was completed, the reaction was continued for 2 h, and then the mixed solution was filtered and the precipitate was fully washed with deionized water until the pH of the filtrate was neutral; (3) The precipitate was dispersed with 1% (w / v) gelatin solution and freeze-dried. After drying, the powder was calcined at 1150°C for 4 h, and the product was mechanically crushed to obtain magnesium phosphate nanoparticles.
6. A magnesium phosphate nanoparticle prepared according to any one of claims 1-5.
7. Application of the magnesium phosphate nanoparticles according to claim 6 in biomedicine, modern agriculture, electrode materials, and sewage treatment.