阅读说明：本技术 一种用花生油制备羟基磷灰石超长纳米线的方法 (Method for preparing hydroxyapatite ultra-long nanowires from peanut oil ) 是由 朱英杰 陈昱桥 于 2021-10-21 设计创作，主要内容包括：本发明涉及一种用花生油制备羟基磷灰石超长纳米线的方法。该羟基磷灰石超长纳米线的制备方法为：采用花生油、醇、强碱水溶液、水溶性钙盐和水溶性磷酸盐作为原料制成前驱体悬浮液,经过溶剂热反应,制备得到羟基磷灰石超长纳米线；所述羟基磷灰石超长纳米线的直径为2～200 nm,长度为20～1000μm。(The invention relates to a method for preparing a hydroxyapatite ultralong nanowire from peanut oil. The preparation method of the hydroxyapatite ultralong nanowire comprises the following steps: preparing a precursor suspension by using peanut oil, alcohol, a strong alkali aqueous solution, a water-soluble calcium salt and a water-soluble phosphate as raw materials, and performing solvothermal reaction to prepare the hydroxyapatite ultralong nanowire; the diameter of the hydroxyapatite ultralong nanowire is 2-200 nm, and the length of the hydroxyapatite ultralong nanowire is 20-1000 microns.)

1. A preparation method of a hydroxyapatite ultra-long nanowire is characterized in that peanut oil, alcohol, a strong alkali aqueous solution, a water-soluble calcium salt and a water-soluble phosphate are used as raw materials to prepare a precursor suspension, and the precursor suspension is subjected to solvothermal reaction to prepare the hydroxyapatite ultra-long nanowire; the diameter of the hydroxyapatite ultralong nanowire is 2-200 nm, and the length of the hydroxyapatite ultralong nanowire is 20-1000 microns.

2. The method of claim 1, comprising:

(1) mixing peanut oil and alcohol, and adding a strong alkali aqueous solution, a water-soluble calcium salt aqueous solution and a water-soluble phosphate aqueous solution under stirring to form a precursor suspension; the alcohol is methanol or/and ethanol;

(2) carrying out solvothermal reaction on the obtained precursor suspension for 1-72 hours at 100-250 ℃ to obtain a product;

(3) and separating the obtained product, and washing with ethanol and water for multiple times to obtain the hydroxyapatite ultralong nanowire.

3. The production method according to claim 1 or 2, wherein the water-soluble phosphate is selected from at least one of sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium tripolyphosphate, potassium hexametaphosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium tripolyphosphate, ammonium hexametaphosphate, and/or hydrates of the above compounds;

the molar concentration of the water-soluble phosphate in the precursor suspension is 0.001-12 mol/L, and preferably 0.01-3 mol/L.

4. The production method according to any one of claims 1 to 3, wherein the water-soluble calcium salt is selected from at least one of calcium chloride, calcium nitrate, calcium acetate, calcium sulfate, and/or a hydrate of the above compound;

the molar concentration of the water-soluble calcium salt in the precursor suspension is 0.001-12 mol/L, and preferably 0.01-3 mol/L.

5. The method according to any one of claims 1 to 4, wherein the strong alkali aqueous solution is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide; the molar concentration of the strong base in the precursor suspension is 0.01-5 mol/L, and preferably 0.1-3 mol/L.

6. A method of preparation according to any one of claims 1 to 5, wherein the peanut oil is present in the precursor suspension at a concentration of between 5% and 40% by weight, preferably between 9% and 20% by weight.

7. A preparation method according to any one of claims 1 to 6, wherein the weight ratio of peanut oil to alcohol is 1:20 to 20: 1;

the weight ratio of the peanut oil to the water-soluble calcium salt is 1: 10-100: 1;

the molar ratio of the water-soluble calcium salt to the water-soluble phosphate is 1: 10-10: 1.

8. A hydroxyapatite ultra-long nanowire prepared according to the preparation method of any one of claims 1 to 7.

9. Use of the hydroxyapatite ultra-long nanowire according to claim 8 in the fields of biomedicine, high temperature resistance, fire resistance, energy, electronic information and environmental protection.

Technical Field

The invention relates to a preparation method of a hydroxyapatite ultralong nanowire, in particular to a method for preparing the hydroxyapatite ultralong nanowire from peanut oil, and belongs to the field of preparation of nano materials.

Background

Hydroxyapatite is an inorganic substance widely existing in nature, is a main inorganic component of hard tissues (bones and teeth) of vertebrates, has excellent biocompatibility and is environment-friendly. The hydroxyapatite material has wide application in the biomedical fields of drug loading and transportation, biological imaging, protein separation, gene transfection, hard tissue defect repair, biological coating, tissue engineering and the like. In the appearances of various hydroxyapatite, the hydroxyapatite super-long nanowire has super-high length-diameter ratio and nano-scale diameter, and can be used as an ideal two-dimensional film material and a construction unit of a three-dimensional material.

However, a large amount of oleic acid or oleate is generally required in the preparation process of the conventional hydroxyapatite ultra-long nanowire, and the oleic acid or oleate is expensive, so that the preparation cost of the hydroxyapatite ultra-long nanowire is high, and the mass production and large-scale application of the hydroxyapatite ultra-long nanowire are limited.

Disclosure of Invention

Aiming at the problems, the invention aims to provide a preparation method of an environment-friendly and low-cost hydroxyapatite ultra-long nanowire, and particularly relates to a preparation method of a hydroxyapatite ultra-long nanowire by using peanut oil.

On one hand, the invention provides a preparation method of a hydroxyapatite ultralong nanowire, which comprises the steps of preparing a precursor suspension by using peanut oil, alcohol, strong base, water-soluble calcium salt and water-soluble phosphate as raw materials, and preparing the hydroxyapatite ultralong nanowire through solvothermal reaction; the diameter of the hydroxyapatite ultralong nanowire is 2-200 nm, and the length of the hydroxyapatite ultralong nanowire is 20-1000 microns.

In the method, water-soluble calcium salt is used as a calcium source, water-soluble phosphate is used as a phosphorus source, peanut oil is used as a template, a surfactant and an emulsifier, a strong alkaline aqueous solution is used as an alkaline environment regulator, water and methanol (or ethanol) are used as solvents, and a reaction precursor suspension is obtained after mixing and stirring at room temperature; and carrying out solvent heat treatment on the obtained reaction precursor suspension, separating, and washing with ethanol and water to obtain the hydroxyapatite ultralong nanowire.

Preferably, the method comprises the following steps:

(1) mixing peanut oil with alcohol, and adding a strong alkali aqueous solution, a water-soluble calcium salt aqueous solution and a water-soluble phosphate aqueous solution under stirring to form a precursor suspension; the alcohol is methanol or/and ethanol;

(2) carrying out solvothermal reaction on the obtained precursor suspension for 1-72 hours at 100-250 ℃ to obtain a product;

(3) and separating the obtained product, and washing with ethanol and water for multiple times to obtain the hydroxyapatite ultralong nanowire.

Preferably, the water-soluble phosphate is at least one selected from sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium tripolyphosphate, potassium hexametaphosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium tripolyphosphate, ammonium hexametaphosphate and/or hydrates of the above compounds;

the molar concentration of the water-soluble phosphate in the precursor suspension is 0.001-12 mol/L, and preferably 0.01-3 mol/L.

Preferably, the water-soluble calcium salt is selected from at least one of calcium chloride, calcium nitrate, calcium acetate, calcium sulfate and/or hydrates of the above compounds;

the molar concentration of the water-soluble calcium salt in the precursor suspension is 0.001-12 mol/L, and preferably 0.01-3 mol/L.

Preferably, the strong base is selected from at least one of sodium hydroxide and potassium hydroxide; the molar concentration of the strong base in the precursor suspension is 0.01-5 mol/L, and preferably 0.1-3 mol/L.

Preferably, the weight percentage concentration of the peanut oil in the precursor suspension is 5-40%, preferably 9-20%.

Preferably, the weight ratio of the peanut oil to the alcohol is 1: 20-20: 1;

the weight ratio of the peanut oil to the water-soluble calcium salt is 1: 10-100: 1;

the molar ratio of the water-soluble calcium salt to the water-soluble phosphate is 1: 10-10: 1.

In another aspect, the present invention provides a hydroxyapatite ultra-long nanowire prepared according to the above preparation method.

In another aspect, the invention also provides an application of the hydroxyapatite ultra-long nanowire in the fields of biomedicine, high temperature resistance, fire resistance, energy, electronic information and environmental protection.

Has the advantages that:

the invention has the outstanding characteristic that the hydroxyapatite ultralong nanowire is prepared from the peanut oil, is environment-friendly and is a green preparation method. Compared with the prior preparation method adopting oleic acid or oleate, the peanut oil has the advantages of lower price, wide source, cost saving and sustainability. The preparation method has the advantages of simple process, low cost, environmental friendliness and the like, is a preparation method suitable for large-scale production, and is expected to be applied in mass production and large scale. The hydroxyapatite super-long nanowire prepared by the method has high length-diameter ratio, good flexibility and good biocompatibility, can be used for preparing high-strength and high-flexibility inorganic refractory paper and three-dimensional functionalized hydroxyapatite nanostructure materials, and has good application prospects in multiple fields.

Drawings

Fig. 1 is a Scanning Electron Microscope (SEM) image of the hydroxyapatite ultra-long nanowire prepared in example 1;

fig. 2 is a Scanning Electron Microscope (SEM) image of the hydroxyapatite ultra-long nanowire prepared in example 2;

fig. 3 is a Scanning Electron Microscope (SEM) image of the hydroxyapatite ultra-long nanowire prepared in example 3;

fig. 4 is an X-ray diffraction (XRD) pattern of the hydroxyapatite nanowires prepared in examples 1 to 3.

Detailed Description

The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.

The invention provides a preparation method of a hydroxyapatite ultralong nanowire, which takes peanut oil as a template, a surfactant and an emulsifier, takes strong base as an alkaline environment regulator, takes water-soluble calcium salt as a calcium source, takes water-soluble phosphate as a phosphorus source, takes water and methanol (or ethanol) as solvents, and obtains a reaction precursor suspension (or called precursor suspension) after mixing and stirring at room temperature; and carrying out solvent heat treatment on the obtained reaction precursor suspension, separating, and washing with ethanol and water to obtain the hydroxyapatite ultralong nanowire. In addition, the peanut oil can be planted every year, and has sustainability. Moreover, the hydroxyapatite ultralong nanowire prepared from the peanut oil has better biocompatibility, the preparation process is more green and environment-friendly, no environmental pollution is caused, and the requirements of sustainable development are met. Therefore, the preparation method has good industrial application prospect.

The diameter of the hydroxyapatite ultralong nanowire prepared by the method can be 2-200 nanometers, and the length of the hydroxyapatite ultralong nanowire can be 20-1000 micrometers.

In an alternative embodiment, the concentration of the peanut oil in the reaction precursor suspension may be between 5% and 40% by weight, preferably between 9% and 20%.

In alternative embodiments, the strong base is selected from at least one of sodium hydroxide, potassium hydroxide; the molar concentration of the strong base in the precursor suspension is 0.01-5 mol/L, and preferably 0.1-3 mol/L.

In alternative embodiments, the water-soluble calcium salt includes, but is not limited to, calcium chloride, calcium nitrate, calcium acetate, calcium sulfate, and/or hydrates thereof, it being understood that one water-soluble calcium salt may be used, and mixtures of two or more water-soluble calcium salts may also be used; in addition, hydrates of water-soluble calcium salts, e.g. CaCl, may also be used₂·2H₂And O. The molar concentration of the water-soluble calcium salt in the reaction precursor suspension can be 0.001-12 mol/L, and preferably 0.01-3 mol/L.

In alternative embodiments, the water-soluble phosphorus source includes, but is not limited to, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium tripolyphosphate, potassium hexametaphosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium tripolyphosphate, ammonium hexametaphosphate, and/or hydrates of the above compounds. One water-soluble phosphate can be adopted, and the mixture of two or more water-soluble phosphates can also be adopted; in addition, hydrates of water-soluble phosphates, such as NaH, may be employed₂PO₄·2H₂And O. The molar concentration of the water-soluble phosphate in the reaction precursor suspension can be 0.001-12 mol/L, and preferably 0.01-3 mol/L.

In the invention, the weight ratio of the peanut oil to the methanol (or ethanol) can be 1: 20-20: 1. The weight ratio of the peanut oil to the water-soluble calcium salt can be 1: 10-100: 1. The molar ratio of the water-soluble calcium salt to the water-soluble phosphate can be 1: 10-10: 1, and preferably, the molar ratio can be 1: 2-2: 1.

In the invention, the temperature of the solvent heat treatment is 100-250 ℃, and preferably 180-210 ℃.

In the present invention, the solvent heat treatment time is 1 to 72 hours, preferably 20 to 48 hours.

In the invention, the product obtained after the heat treatment of the solvent is separated to obtain the hydroxyapatite ultralong nanowire; the separation method comprises centrifugal separation, filtration, standing, precipitation separation and the like.

In the invention, the hydroxyapatite nanowire obtained after the heat treatment of the solvent is washed by ethanol and water, the times of the ethanol and water washing are determined according to requirements, and the hydroxyapatite nanowire is washed by the ethanol and the water for 2-3 times respectively.

The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.

Example 1

At room temperature, 0.333 g of CaCl₂Dissolving in 15 ml of deionized water to form a solution A;

mixing 6.552 g (about 7.5mL) peanut oil, 6 mL methanol, 13.5 mL deionized water to form solution B;

during the stirring, 15 ml of an aqueous solution containing 1.050g of sodium hydroxide was added to the solution B, and after stirring at room temperature for 20 minutes, the solution a was dropwise added to the mixed solution of the solution B and the aqueous sodium hydroxide solution, and after stirring at room temperature for 20 minutes, 15 ml of an aqueous solution containing 0.935g of sodium dihydrogenphosphate dihydrate was added, and stirring was continued for 20 minutes, to obtain a reaction precursor suspension. The weight percentage concentration of peanut oil in the obtained reaction precursor suspension is about 9.1 percent, the concentration of water-soluble phosphate is about 0.085moL/L, and the concentration of water-soluble calcium salt is about 0.042 moL/L;

transferring the reaction precursor suspension into a 100 ml reaction kettle, sealing, carrying out solvent heat treatment at 180 ℃ for 24 hours, and then naturally cooling to room temperature to obtain a product;

centrifuging the product, and washing with deionized water and ethanol for 2 times respectively to obtain hydroxyapatite ultralong nanowire shown in figure 1, wherein the X-ray diffraction (XRD) result shows that the product contains hydroxyapatite as shown in figure 4 (a).

Example 2

At room temperature, 0.333 g of CaCl₂Dissolving in 15 ml of deionized water to form a solution A;

9.360 g (about 10.7mL) peanut oil, 6 mL methanol, 13.5 mL deionized water were mixed to form solution B;

during the stirring, 15 ml of an aqueous solution containing 1.050g of sodium hydroxide was added to the solution B, and after stirring at room temperature for 20 minutes, the solution a was dropwise added to the mixed solution of the solution B and the aqueous sodium hydroxide solution, and after stirring at room temperature for 20 minutes, 15 ml of an aqueous solution containing 0.935g of sodium dihydrogenphosphate dihydrate was added, and stirring was continued for 20 minutes, to obtain a reaction precursor suspension. The weight percentage concentration of the peanut oil in the obtained reaction precursor suspension is about 12.6 percent, the concentration of the water-soluble phosphate is about 0.081moL/L, and the concentration of the water-soluble calcium salt is about 0.040 moL/L;

transferring the reaction precursor suspension into a 100 ml reaction kettle, sealing, carrying out solvent heat treatment at 180 ℃ for 24 hours, and then naturally cooling to room temperature to obtain a product;

the obtained product is centrifugally separated and washed with deionized water and ethanol for 2 times respectively to obtain the hydroxyapatite ultra-long nanowire shown in figure 2, and the X-ray diffraction (XRD) result shows that the component of the product is hydroxyapatite, as shown in figure 4 (b).

Example 3

At room temperature, 0.665 g of CaCl₂Dissolving in 15 ml of deionized water to form a solution A;

9.360 g (about 10.7mL) peanut oil, 6 mL methanol, 13.5 mL deionized water were mixed to form solution B;

during the stirring, 15 ml of an aqueous solution containing 1.050g of sodium hydroxide was added to the solution B, and after stirring at room temperature for 20 minutes, the solution a was dropwise added to the mixed solution of the solution B and the aqueous sodium hydroxide solution, and after stirring at room temperature for 20 minutes, 15 ml of an aqueous solution containing 0.935g of sodium dihydrogenphosphate dihydrate was added, and stirring was continued for 20 minutes, to obtain a reaction precursor suspension. The weight percentage concentration of the peanut oil in the obtained reaction precursor suspension is about 12.5 percent, the concentration of the water-soluble phosphate is about 0.081moL/L, and the concentration of the water-soluble calcium salt is about 0.081 moL/L;

transferring the reaction precursor suspension into a 100 ml reaction kettle, sealing, carrying out solvent heat treatment at 180 ℃ for 24 hours, and then naturally cooling to room temperature to obtain a product;

the obtained product is centrifugally separated and washed with deionized water and ethanol for 2 times respectively to obtain the hydroxyapatite ultra-long nanowire shown in figure 3, and the X-ray diffraction (XRD) result shows that the component of the product is hydroxyapatite, as shown in figure 4 (c).

Industrial applicability: the preparation method has the advantages of simple process, low cost, environmental friendliness and the like, and is suitable for large-scale production. The hydroxyapatite super-long nanowire prepared by the invention has good biocompatibility, high length-diameter ratio and good flexibility, and is an excellent raw material for constructing a macroscopically assembled two-dimensional film or three-dimensional block hydroxyapatite functional material. The hydroxyapatite ultralong nanowire prepared by the invention can be used for preparing high-strength and high-flexibility inorganic refractory paper and high-performance three-dimensional hydroxyapatite functional materials, and has good application prospects in the fields of biomedicine, high temperature resistance, fire resistance, energy, electronic information, environmental protection and the like.