CN111377473A - Monodisperse bionic pollen-shaped calcium carbonate nano material with porous polycrystalline structure and preparation method thereof - Google Patents
Monodisperse bionic pollen-shaped calcium carbonate nano material with porous polycrystalline structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a monodisperse bionic pollen-shaped calcium carbonate nano material with a porous polycrystalline structure and a preparation method thereof, the calcium carbonate nano material is a calcium carbonate nano material with uneven surface and similar appearance of pollen or virus in nature, and the size of nano particles is as follows: length of 150-550nm, width of 80-150nm, specific surface area of 60-170m2The calcium carbonate nano material has mesopores with the size of 2-10 nm. Compared with the prior art, the preparation process of the invention has simple operation, does not need additional complex conditions, does not need power stirring, can react by static placement, has cheap and easily obtained practical raw materials, thereby leading the preparation cost of the material to be relatively low, and the prepared calcium carbonate can be used as plastic modification, biological medicine carrier and the likeHas multiple uses.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a monodisperse bionic pollen-shaped calcium carbonate nano material with a porous and polycrystalline structure and a preparation method thereof.
Background
Calcium carbonate is an important inorganic filler, has the advantages of low price, no toxicity, no irritation, good color and luster, high whiteness and the like, is widely applied to rubber, plastic, paper, food and other industries, and is used as a high-quality filler and white pigment, and the dosage of the calcium carbonate in fine chemical engineering is increased year by year. The nano calcium carbonate is a novel superfine solid material developed in the 80 th of the 20 th century, has the particle size of 1-100 nm, is a novel high-grade functional inorganic material, and shows wide applicability and vigorous market demand of products. The application performance of the nano calcium carbonate mainly depends on the chemical composition, morphological characteristics, particle size, dispersion degree and the like. Among them, the particle size distribution and the degree of dispersion of calcium carbonate particles are very important factors. Only the nano calcium carbonate material with uniform particle size distribution and good dispersion degree has the nano effect to be fully reflected, and the product has better application performance and scientific and technological added value, so that the preparation of the nano calcium carbonate with good dispersion and regular appearance becomes a hotspot for the development of the nano material industry. In recent years, calcium carbonate-based materials have been increasingly valued by researchers for their excellent biocompatibility. The nano calcium carbonate can be used for producing antibiotics and has certain pharmacological action in stomach drugs and analgesics. In addition, the nano calcium carbonate can also be used as a drug carrier with excellent performance, and relates to disease treatment, targeted drug loading and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a monodisperse bionic pollen-shaped calcium carbonate nano material with a porous polycrystalline structure and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme: a monodisperse bionic pollen-shaped calcium carbonate nano material with a porous polycrystalline structure is characterized in that the calcium carbonate nano material is a calcium carbonate nano material with uneven surface and similar appearance of pollen or viruses in nature, and the size of nano particles is as follows: length of 150-550nm, width of 80-150nm, specific surface area of 60-170m2The calcium carbonate nano material has mesopores with the size of 2-10 nm.
The preparation method of the monodisperse porous and polycrystalline bionic pollen-shaped calcium carbonate nano material is characterized in that a precursor calcium salt and alkali are dissolved in an organic solvent, carbon dioxide is slowly introduced through decomposition of decomposable carbonate or bicarbonate, and the monodisperse porous and polycrystalline bionic pollen-shaped calcium carbonate nano material is obtained through a precipitation reaction process occurring at a gas phase interface and a liquid phase interface. The method comprises the following specific steps:
(1) dissolving a certain amount of precursor calcium salt and alkali in an organic solvent, obtaining a clear mixed solution by ultrasonic dispersion or magnetic stirring, sealing a container A of the solution by using a sealing film, and leaving a plurality of small holes on the sealing film;
(2) placing the easily decomposed carbonate in a container B, sealing the container B with a sealing film, and pricking holes;
(3) and (3) placing the container A and the container B in a large-volume container C, simultaneously placing a certain amount of water-absorbing silica gel in the large container C, sealing the container C, standing the container C until the solution in the container A generates white precipitate, and then performing centrifugal separation and washing on the obtained precipitate to obtain the porous and polycrystalline bionic pollen-shaped calcium carbonate nano material.
In the invention, calcium salt is subjected to polycondensation reaction in the presence of alkali to generate calcium hydroxide sol, and the calcium hydroxide is further reacted with carbon dioxide generated by decomposing carbonate or bicarbonate to generate the porous, polycrystalline and bionic pollen-shaped calcium carbonate nanorod material.
The organic solvent is one or more of liquid straight-chain alkyl alcohol or isomer alcohol thereof, liquid straight-chain alkane or naphthene, liquid organic olefin, aromatic hydrocarbon, tetrahydrofuran, chloroform, dichloromethane and diethyl ether; the organic solvent is one or more of ethanol, methanol, propanol, isopropanol, n-butanol, benzyl alcohol, diethyl ether, hexane, cyclohexane, benzene, toluene, xylene, chloroform, and diethyl ether.
The precursor calcium salt is one or more of an organic calcium salt precursor or an inorganic calcium salt precursor which can be dissolved in an organic solvent; the organic calcium salt precursor is obtained by chelating and coordinating calcium ions with an organic ligand, and the inorganic calcium salt precursor is calcium chloride, calcium nitrate or calcium perchlorate; the precursor calcium salt is one or more of calcium chloride, calcium nitrate, calcium acetate, calcium gluconate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium silicate, calcium superphosphate, calcium citrate, calcium pyrophosphate, calcium laurate, calcium lactate, calcium acetylacetonate, calcium ethylenediaminetetraacetate and calcium tartrate.
The alkali is organic alkali or inorganic alkali; the organic alkali is organic amine; the organic base is methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine or hexamethylenetetramine, and the inorganic base is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide or ammonia water.
The easily decomposed carbonate is inorganic carbonate or bicarbonate; the easily decomposed carbonate is one or more of ammonium carbonate, sodium carbonate, ammonium bicarbonate, potassium bicarbonate and sodium bicarbonate.
The concentration of the calcium salt in the solution in the vessel A in the reaction system is in the range of 5 to 15% by weight, preferably 5 to 10% by weight; the mass ratio of the precursor calcium salt to the added alkali is 5-100: 1, preferably 5 to 50: 1; the reaction period ranges from 1 to 3 days; the reaction temperature is controlled at room temperature, namely, the range is controlled between 5 and 40 ℃ along with seasonal change.
The container A, the container B and the container C are glass containers or organic plastic containers and comprise one or more of a glass flask, a glass beaker, a watch glass, a conical flask, a wide-mouth bottle, a weighing bottle, a test tube, a measuring cup, a plastic beaker and a centrifuge tube.
The selected ultrasonic vibration dissolution dispersion power range in the step (1) is 100-400W.
The centrifugal speed of the centrifugal separation in the step (3) is 5000-12000rpm, and the time of each centrifugation is 3-10 min; among them, the control of the centrifugal rotation speed is preferably 8000-.
The solvent selected for washing is one or more of water, ethanol, acetone, diethyl ether, cyclohexane and n-hexane.
The selected sealing film material is one or more of polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyvinyl chloride and polyvinylidene chloride.
Compared with the prior art, the calcium carbonate nano material in the nano bionic flower powder is prepared by reacting a calcium salt precursor in an organic solvent with alkali to generate calcium hydroxide sol and then slowly reacting with carbon dioxide released by decomposable carbonate or bicarbonate. Compared with the traditional calcium salt and direct carbonization synthesis method by introducing carbon dioxide, the method has the advantages of strong controllability, simple process, convenient operation and low cost. The whole preparation reaction process is carried out under the static condition at room temperature, the nano calcium carbonate obtained by energy conservation and environmental protection has the appearance similar to pollen or virus in nature, uneven surface, a plurality of protrusions, good monodispersity, uniform granularity, accurate and controllable size, and wide application prospect, and is particularly applied to the field of biological medicine.
Drawings
FIG. 1 is a characteristic projection Transmission Electron Microscope (TEM) image of a monodisperse, porous, polycrystalline structure, biomimetic pollen-like calcium carbonate nanomaterial made from example 1.
FIG. 2 is a characteristic large-angle X-ray spectrum of a monodisperse calcium carbonate nanorod material with a porous and polycrystalline structure, which is obtained in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Dissolving a certain amount of calcium chloride by using 100 pure ethanol, carrying out ultrasonic treatment for 20min, adding 0.08g of solid sodium hydroxide into the solution, continuing the ultrasonic treatment for 10min, thus adjusting the pH value of the solution to be about 14, sealing a container of the solution by using a preservative film, and leaving 150 small holes on the preservative film. And simultaneously, putting the ammonium bicarbonate solid into another beaker, placing the beaker with an opening, then putting the two beakers into a large-volume beaker with a certain amount of silica gel drying agent spread at the bottom, sealing the beaker by using a preservative film, and then standing the beaker and placing the reaction system. After reacting for about 96 hours, centrifugally separating the white precipitate generated in the solution, and washing with ethanol to obtain the porous, polycrystalline and bionic flower powder calcium carbonate nano material. The characteristic projection Transmission Electron Microscope (TEM) image of the obtained calcium carbonate nano material shows that the calcium carbonate nano material is monodisperse, has porous and polycrystalline structure and uneven surface and is similar to the appearance of pollen or virus in the nature as shown in fig. 1, and shows that the calcium carbonate nano particle material with the porous and polycrystalline structure has a characteristic large-angle X-ray spectrogram as shown in fig. 2, and the prepared calcium carbonate nano particle has relatively high crystallization degree, and a plurality of crystal phases with different structures exist in the particle at the same time.
Example 2
Dissolving a certain amount of calcium chloride by using 100 pure ethanol, carrying out ultrasonic treatment for 20min, adding 0.08g of solid sodium hydroxide into the solution, continuing the ultrasonic treatment for 10min, thus adjusting the pH value of the solution to be about 14, sealing a container of the solution by using a preservative film, and leaving 80 small holes on the preservative film. And simultaneously, putting the ammonium bicarbonate solid into another beaker, placing the beaker with an opening, then putting the two beakers into a large-volume beaker with a certain amount of silica gel drying agent spread at the bottom, sealing the beaker by using a preservative film, and then standing the beaker and placing the reaction system. After reaction for about 96 hours, the white precipitate generated in the solution is centrifugally separated and washed by ethanol, and the porous, polycrystalline and bionic flower powdery calcium carbonate nano material with smaller particle size can be obtained.
Example 3
Dissolving a certain amount of calcium chloride by using 100 pure ethanol, carrying out ultrasonic treatment for 20min, adding 0.08g of solid sodium hydroxide into the solution, continuing the ultrasonic treatment for 10min, thus adjusting the pH value of the solution to be about 14, sealing a container of the solution by using a preservative film, and leaving 80 small holes on the preservative film. And simultaneously, putting the ammonium bicarbonate solid into another beaker, placing the beaker with an opening, then putting the two beakers into a large-volume beaker with a certain amount of silica gel drying agent spread at the bottom, sealing the beaker by using a preservative film, and then standing the beaker and placing the reaction system. After about 48 hours of reaction, the white precipitate formed in the solution was centrifuged and washed with ethanol to obtain a porous, polycrystalline, and bionic flower-like calcium carbonate nanomaterial having a smaller particle size than that of example 2.
Example 4
Dissolving a certain amount of calcium chloride by using 100 pure ethanol, carrying out ultrasonic treatment for 20min, adding 0.03g of solid sodium hydroxide into the solution, continuing the ultrasonic treatment for 10min, thus adjusting the pH value of the solution to be about 11, sealing a container of the solution by using a preservative film, and leaving 150 small holes on the preservative film. And simultaneously, putting the ammonium bicarbonate solid into another beaker, placing the beaker with an opening, then putting the two beakers into a large-volume beaker with a certain amount of silica gel drying agent spread at the bottom, sealing the beaker by using a preservative film, and then standing the beaker and placing the reaction system. After reaction for about 96 hours, the white precipitate generated in the solution is centrifugally separated and washed by ethanol, and the porous, polycrystalline and rod-shaped calcium carbonate nano material can be obtained.
Example 5
Dissolving a certain amount of calcium chloride with 100 pure isopropanol, carrying out ultrasonic treatment for 20min, adding 0.08g of solid sodium hydroxide into the solution, continuing the ultrasonic treatment for 10min, thus adjusting the pH value of the solution to be about 14, sealing a container of the solution by using a preservative film, and leaving 80 small holes on the preservative film. And simultaneously, putting the ammonium bicarbonate solid into another beaker, placing the beaker with an opening, then putting the two beakers into a large-volume beaker with a certain amount of silica gel drying agent spread at the bottom, sealing the beaker by using a preservative film, and then standing the beaker and placing the reaction system. After about 48h of reaction, the white precipitate formed in the solution was centrifuged and washed with ethanol to obtain porous, polycrystalline, and bionic flower-like calcium carbonate nanomaterial similar in size to that of example 1.
Example 6
The preparation method of the monodisperse porous and polycrystalline bionic pollen-shaped calcium carbonate nano material comprises the following specific steps:
(1) dissolving a certain amount of precursors, namely calcium dihydrogen phosphate and alkali methylamine, in an organic solvent tetrahydrofuran, wherein the concentration of the calcium salt precursor is 0.1 wt%, and the mass ratio of the calcium salt precursor to the alkali is 0.1: 1, obtaining a clear mixed solution by ultrasonic dispersion within the power range of 100-;
(2) putting the easily decomposed potassium bicarbonate carbonate into a container B, sealing the container B by using a sealing film, and pricking holes;
(3) placing the container A and the container B in a large-volume container C, simultaneously placing a certain amount of water-absorbing silica gel in the large container C and sealing the water-absorbing silica gel, standing the container C for 1 day until the solution in the container A generates white precipitate, then centrifugally separating and washing the obtained precipitate, wherein the centrifugal rotating speed is 5000rpm, and the solvent used in washing is water, thus obtaining the bionic pollen-shaped calcium carbonate nano material with a porous and polycrystalline structure. Nanoparticle size: the length is 150-550nm, and the width is 80-150 nm; the mesoporous size is between 2 and 10nm, and the specific surface area is between 60 and 170m2/g。
Example 7
The preparation method of the monodisperse porous and polycrystalline bionic pollen-shaped calcium carbonate nano material comprises the following specific steps:
(1) dissolving a certain amount of precursors, namely calcium dihydrogen phosphate and alkali methylamine, in an organic solvent tetrahydrofuran, wherein the concentration of the calcium salt precursor is 10 wt%, and the mass ratio of the calcium salt precursor to the alkali is 100: 1, obtaining a clear mixed solution by ultrasonic dispersion within the power range of 100-;
(2) putting the easily decomposed potassium bicarbonate carbonate into a container B, sealing the container B by using a sealing film, and pricking holes;
(3) placing the container A and the container B in a large-volume container C, simultaneously placing a certain amount of water-absorbing silica gel in the large container C, sealing the container C, standing for 3 days until the solution in the container A generates white precipitate, then performing centrifugal separation and washing on the obtained precipitate, wherein the centrifugal rotation speed is 12000rpm, and the solvent used in the washing is water, so that the bionic pollen-shaped calcium carbonate nano material with a porous and polycrystalline structure is obtained. Nanoparticle size: the length is 150-550nm, and the width is 80-150 nm; the mesoporous size is between 2 and 10nm, and the specific surface area is between 60 and 170m2/g。
Claims (10)
1. A monodisperse bionic pollen-shaped calcium carbonate nano material with a porous polycrystalline structure is characterized in that the calcium carbonate nano material is a calcium carbonate nano material with uneven surface and similar appearance of pollen or viruses in nature, and the size of nano particles is as follows: length of 150-550nm, width of 80-150nm, specific surface area of 60-170m2The calcium carbonate nano material has mesopores with the size of 2-10 nm.
2. The preparation method of the monodisperse bionic pollen-shaped calcium carbonate nanomaterial with a porous polycrystalline structure as claimed in claim 1, is characterized by comprising the following steps:
(1) dissolving a certain amount of precursor calcium salt and alkali in an organic solvent, obtaining a clear mixed solution by ultrasonic dispersion or magnetic stirring, sealing a container A of the solution by using a sealing film, and leaving a plurality of small holes on the sealing film;
(2) placing the easily decomposed carbonate in a container B, sealing the container B with a sealing film, and pricking holes;
(3) and (3) placing the container A and the container B in a large-volume container C, simultaneously placing a certain amount of water-absorbing silica gel in the large container C, sealing the container C, standing the container C until the solution in the container A generates white precipitate, and then performing centrifugal separation and washing on the obtained precipitate to obtain the porous and polycrystalline bionic pollen-shaped calcium carbonate nano material.
3. The preparation method of the monodisperse porous polycrystalline structure bionic pollen-shaped calcium carbonate nano material as claimed in claim 2, wherein the organic solvent is one or more of liquid linear alkyl alcohol or isomer alcohol thereof, liquid linear alkane or cycloalkane, liquid organic olefin, aromatic hydrocarbon, tetrahydrofuran, chloroform, dichloromethane and diethyl ether;
the precursor calcium salt is one or more of an organic calcium salt precursor or an inorganic calcium salt precursor which can be dissolved in an organic solvent; the organic calcium salt precursor is obtained by chelating and coordinating calcium ions with an organic ligand, and the inorganic calcium salt precursor is calcium chloride, calcium nitrate or calcium perchlorate;
the alkali is organic alkali or inorganic alkali; the organic alkali is organic amine;
the easily decomposed carbonate is inorganic carbonate or bicarbonate;
the concentration range of calcium salt in the reaction system solution is 5-15 wt%; the mass ratio of the precursor calcium salt to the added alkali is 5-100: 1; the reaction period ranges from 1 to 3 days; the reaction temperature is controlled at room temperature, namely, the range is controlled between 5 and 40 ℃ along with seasonal change.
4. The method for preparing the monodisperse bionic pollen-shaped calcium carbonate nanomaterial with a porous polycrystalline structure according to claim 2 or 3, wherein the precursor calcium salt is one or more of calcium chloride, calcium nitrate, calcium acetate, calcium gluconate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium silicate, calcium superphosphate, calcium citrate, calcium pyrophosphate, calcium laurate, calcium lactate, calcium acetylacetonate, calcium ethylenediaminetetraacetate and calcium tartrate.
5. The preparation method of the monodisperse porous polycrystalline structure bionic pollen-shaped calcium carbonate nano material as claimed in claim 2 or 3, wherein the organic base is methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine or hexamethylenetetramine, and the inorganic base is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide or ammonia water.
6. The preparation method of the monodisperse porous polycrystalline structure bionic pollen-shaped calcium carbonate nano material as claimed in claim 2 or 3, wherein the easily decomposable carbonate is one or more of ammonium carbonate, sodium carbonate, ammonium bicarbonate, potassium bicarbonate and sodium bicarbonate.
7. The preparation method of the monodisperse porous polycrystalline structure bionic pollen-shaped calcium carbonate nano material as claimed in claim 2 or 3, wherein the organic solvent is one or more of ethanol, methanol, propanol, isopropanol, n-butanol, benzyl alcohol, diethyl ether, hexane, cyclohexane, benzene, toluene, xylene, trichloromethane and diethyl ether.
8. The preparation method of the monodisperse porous polycrystalline structure bionic pollen-shaped calcium carbonate nanomaterial, as claimed in claim 2 or 3, wherein the containers A, B and C are glass containers or organic plastic containers, and comprise one or more of glass flasks, glass beakers, watch-flasks, wide-mouthed bottles, weighing bottles, test tubes, measuring cups, plastic beakers and centrifuge tubes.
9. The method for preparing the monodisperse porous bionic pollen-shaped calcium carbonate nanomaterial with the polycrystalline structure as claimed in claim 2, wherein the ultrasonic dispersion selected in the step (1) is ultrasonic vibration dissolution dispersion, and the power range is 100-400W;
the centrifugal speed of the centrifugal separation in the step (3) is 5000-12000rpm, and the time of each centrifugation is 3-10 min;
and (3) selecting one or more solvents from water, ethanol, acetone, diethyl ether, cyclohexane and n-hexane for washing.
10. The preparation method of the monodisperse porous polycrystalline structure bionic pollen-shaped calcium carbonate nano material as claimed in claim 2 or 3, wherein the sealing film material is one or more of polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyvinyl chloride and polyvinylidene chloride.
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| CN112374518A (en) * | 2020-11-06 | 2021-02-19 | 南通大学 | Preparation method and application of nano calcium carbonate |
| CN113716594A (en) * | 2021-08-27 | 2021-11-30 | 杭州师范大学 | Preparation method of hollow calcium carbonate nanoparticles and double-additive mediated hollow calcium carbonate nanoparticles |
| CN114149190A (en) * | 2020-08-18 | 2022-03-08 | 中山职业技术学院 | Preparation method of high-biocompatibility alpha-tricalcium phosphate nano powder for 3D printing |
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