CN113716594A - Preparation method of hollow calcium carbonate nanoparticles and double-additive mediated hollow calcium carbonate nanoparticles - Google Patents
Preparation method of hollow calcium carbonate nanoparticles and double-additive mediated hollow calcium carbonate nanoparticles Download PDFInfo
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Abstract
The invention relates to the technical field of chemical materials, in particular to a preparation method of hollow calcium carbonate nano-particles and double-additive mediated hollow calcium carbonate nano-particles, which comprises the following steps: (1) dissolving a precursor calcium salt and dopamine hydrochloride in an alcohol solution, adding sodium citrate into the alcohol solution, and performing ultrasonic mixing to obtain a mixed solution; (2) and placing the mixed solution in a container A sealed by aluminum foil paper with holes, placing the mixed solution and a container B filled with ammonium bicarbonate in a sealed jacket reactor adjacently, and performing reaction and post-treatment to obtain the hollow calcium carbonate nanoparticles. According to the invention, the complexation effect of sodium citrate on calcium ions and the self-polymerization effect of dopamine are utilized for the first time, the morphology and growth of calcium carbonate are synergistically regulated, the crystallization growth process of calcium carbonate particles is more controllable, stable and efficient, and the obtained product particles have the advantages of good hollow structure, uniform particle size, large specific surface area, good dispersibility and the like.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a hollow calcium carbonate nano-particle and a preparation method of a double-additive mediated hollow calcium carbonate nano-particle.
Background
Calcium carbonate is one of the most widely existing minerals in the nature, has the characteristics of low price, no toxicity, good biocompatibility and the like, and is widely applied to the industries of plastics, papermaking, coatings, ceramics, medicines and the like. In the field of nano medicine, calcium carbonate nanoparticles have the characteristics of good biocompatibility, degradability, nontoxicity and the like, and particularly porous or hollow calcium carbonate nanoparticles have large specific surface area, are used for the research of constructing nano medicine delivery carriers and integrating diagnosis and treatment, and open up a brand new direction in the field of nano medicine.
The particle size, the dispersion degree, the appearance and the crystal form of the calcium carbonate nano material determine the performance and the application of the calcium carbonate nano material, so that the calcium carbonate nano material is very important for the controllable synthesis of calcium carbonate. The main methods for synthesizing the calcium carbonate nano material include an emulsification technology method, a chemical precipitation method, a biomineralization method and the like.
CN 111762807A discloses a preparation method of hollow microsphere calcium carbonate, which comprises the following steps: dissolving calcium oxide in deionized water to obtain calcium hydroxide slurry with the raw material of 2%; then transferring the calcium hydroxide slurry into a high-pressure reaction kettle, adding 2-10% of EDTA, and reacting at 80-160 ℃ for 4h to obtain product slurry; and (3) carrying out suction filtration and washing on the product slurry, carrying out vacuum drying on the obtained solid at the temperature of 80 ℃ for 10h, and finally grinding the obtained solid into powder to obtain the hollow microsphere calcium carbonate.
CN 111017973 a discloses a method for preparing hollow nano calcium carbonate by using ultrasonic aerosol, 1) drying carbon dioxide; 2) metering of carbon dioxide; 3) heating carbon dioxide; 4) and (4) carbonizing the calcium hydroxide liquid drops. The hollow nano calcium carbonate prepared by the method can be used as carrier particles for coating other components; the method comprises the steps of generating calcium hydroxide solution aerosol by calcium hydroxide emulsion liquid drops in an ultrasonic aerosol generating device in a dry heat and excessive carbon dioxide atmosphere, generating calcium carbonate crystals on the surfaces of the aerosol liquid drops to form shell layers, evaporating the surface water of the calcium hydroxide emulsion liquid drops in a carbonization process, dehydrating the calcium hydroxide emulsion liquid drops, and finally forming the hollow nano calcium carbonate.
The calcium carbonate nano-particles prepared by the traditional method have poor structure controllability, wide particle size distribution and poor stability, and are difficult to obtain uniform appearance and/or single crystal form. In addition, calcium carbonate prepared by different methods has different structures and crystal forms, has larger appearance difference, and is difficult to disperse due to agglomeration, which is an important difficult problem to be solved urgently in the production and research process of the nano calcium carbonate at present.
Disclosure of Invention
The invention aims to solve the problems of large shape difference, nonuniform particle size and difficult dispersion of agglomeration of nano calcium carbonate in the prior art, and provides a method for preparing hollow amorphous calcium carbonate nano particles by using a double-additive mediation.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of double-additive mediated hollow calcium carbonate nanoparticles is characterized by comprising the following steps:
(1) dissolving a precursor calcium salt and dopamine hydrochloride in an alcohol solution, adding sodium citrate into the alcohol solution, and performing ultrasonic mixing to obtain a mixed solution;
(2) and placing the mixed solution in a container A sealed by aluminum foil paper with holes, placing the container A and a container B filled with ammonium bicarbonate in a sealed jacket reactor adjacently, reacting the reactor in a stirring manner until the mixed solution turns blue, taking out the mixed solution, and centrifuging and washing the mixed solution to obtain the hollow calcium carbonate nano-particles.
Firstly, dissolving a precursor calcium salt, dopamine hydrochloride and sodium citrate in an alcohol solution, slowly introducing carbon dioxide and ammonia gas through thermal decomposition of ammonium bicarbonate, dissolving and diffusing the gas into the alcohol solution through a gas-liquid phase interface, wherein the dissolved carbon dioxide is used as a carbonate source, and the dissolved ammonia gas is used as an alkaline environment source for self-polymerization of dopamine. Under the action of continuous stirring, the dopamine in the solution is subjected to self-polymerization, and simultaneously the calcium carbonate nucleation growth process synergistically regulated by the poly-dopamine and the sodium citrate is promoted, so that the monodisperse hollow calcium carbonate nanoparticles are obtained.
The precursor calcium salt comprises one of calcium chloride dihydrate, calcium nitrate, calcium acetate and calcium perchlorate, and the alcohol solution comprises one of methanol, ethanol, propanol and butanol.
Preferably, in the step (1), the mass ratio of the precursor calcium salt to the dopamine hydrochloride is 150: (1-16);
the concentration of the precursor calcium salt in the mixed solution is 0.01-0.2 wt%;
the concentration of the dopamine hydrochloride in the mixed solution is 0.1-1mM, and the concentration of the dopamine hydrochloride directly influences the size of the hollow structure of the final calcium carbonate nano-particles.
Preferably, in the step (1), the concentration of the sodium citrate in the mixed solution should be not higher than 10mM, the sodium citrate mainly plays an important role in the dispersibility and the particle size of the sodium carbonate nanoparticles, and the high concentration of the sodium citrate is easy to cause the agglomeration growth of the hollow calcium carbonate nanoparticles, and the dispersibility is poor.
Preferably, in step (1), the concentration of sodium citrate in the mixed solution should be not less than 1.0mM, and too low concentration thereof results in calcium carbonate nanoparticles having too small a size and insignificant hollow structure.
Further preferably, in the step (1), the concentration of the sodium citrate in the mixed solution is 1.25 to 5.0 mM. The calcium carbonate nanoparticles prepared in the range have uniform size and a proper hollow structure size.
In the step (1), the ultrasonic power is 50-200W, the ultrasonic time is 3-15min, and the ultrasonic frequency is 20-60KHz, so that the raw materials are fully dispersed.
In the step (2), the mass-to-volume ratio of the ammonium bicarbonate to the mixed solution is 1-10g:50 mL.
In the step (2), the reaction temperature is 40-60 ℃, and the reaction time is 2-4 h;
the number of the openings of the aluminum foil paper is 30-100, and the aperture is 5-20 mm.
The temperature and time of the reactor and the number of the holes on the aluminum foil paper on the surface of the mixed solution are all used for controlling the introduction amount of carbon dioxide and ammonia gas, when the reaction temperature is higher, the thermal decomposition of ammonium bicarbonate is faster, the generated carbon dioxide and ammonia gas are also faster, and the speed of entering the mixed solution is faster.
In the step (2), the centrifugation time is 5-20min, and the centrifugation speed is 4000-8000 rpm; washing with alcohol solution for 2-5 times. And (3) removing excessive unreacted raw materials and solvents by post-treatment of the product to obtain the hollow calcium carbonate nano-particles.
The invention also provides the hollow calcium carbonate nano-particles prepared by the preparation method, wherein the particle size of the hollow calcium carbonate nano-particles is 70-180 nm, and the specific surface area is 60-170m2And/g, has a pore structure with the size of 3-30 nm.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the complexing action of sodium citrate on calcium ions and the self-polymerization of dopamine are utilized for the first time, the morphology and growth of calcium carbonate are synergistically regulated, and compared with a single additive or additive-free regulation method, the double-additive regulation and control method has the advantages that the crystallization growth process of calcium carbonate particles is controllable, stable and efficient, and a new method and thought are provided for the morphology regulation and control of calcium carbonate materials.
(2) The invention can effectively improve and control the hollow structure, granularity and crystal form of the calcium carbonate nano-particles by regulating and controlling parameters such as the concentration of the additive, the ratio of reactants and the like so as to obtain amorphous calcium carbonate nano-particles with different particle sizes and hollow structures.
(3) The preparation process is rapid and simple, the reaction conditions are mild, the reproducibility is high, and the obtained product particles have the advantages of good hollow structure, uniform particle size, large specific surface area, good dispersibility and the like. Besides the potential application as a high-efficiency drug carrier, the method also has the potential application in the fields of heavy metal ion adsorption and removal and the like.
Drawings
Fig. 1 is a TEM image of hollow calcium carbonate nanoparticles of example 2.
Fig. 2 is an SEM image of the hollow calcium carbonate nanoparticles of example 2.
Fig. 3 is a BET graph of the hollow calcium carbonate nanoparticles of example 2.
Fig. 4 is a PXRD pattern of the hollow calcium carbonate nanoparticles of example 2.
Fig. 5 is a TEM image of the calcium carbonate product obtained in comparative example 4.
Fig. 6 is a TEM image of calcium carbonate nanoparticles prepared in comparative example 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
In the following embodiments, all the raw materials used are purchased from the market and used as they are without treatment.
Example 1
Adding calcium chloride dihydrate (CaCl)2·2H2O) and dopamine hydrochloride (Dop) in a mass ratio of 150: 2, dissolving in 50mL of absolute ethyl alcohol solution, and performing ultrasonic treatment at room temperature for 5min to uniformly mix; adding appropriate amount of sodium citrate to make the final concentration of sodium citrate be 1.25mM, ultrasonic dispersing for 5min to obtain clear mixed solution, and placing the above solution on aluminum foil paperIn the sealed beaker a, 40 small holes were left in the aluminum foil paper. At the same time, 2.5g of ammonium bicarbonate was loaded into the petri dish B and placed open. Placing the beaker A and the culture dish B in a sealed jacket reactor together in an adjacent mode, placing the reactor on a magnetic stirrer, controlling the reaction temperature to be 40 ℃, the stirring speed of the solution in the beaker A to be 200rpm, changing the solution into blue after the reaction time is 4 hours, centrifugally separating the obtained product at the rotating speed of 8000rpm, and washing the product with ethanol for three times to obtain hollow calcium carbonate nanoparticles with the particle size of 70-90 nm and the specific surface area of 78-100m2And/g, has a pore structure with the size of 5-12 nm.
Example 2
Hollow calcium carbonate nanoparticles were prepared according to the procedure of example 1, with the final concentration of sodium citrate controlled at 2.5mM, and other process conditions unchanged.
TEM representation is carried out on the hollow calcium carbonate nanoparticles prepared in the example 2, and the obtained nanoparticles have good hollow structures and better dispersibility as shown in the attached drawing 1. SEM representation is carried out on the hollow calcium carbonate nanoparticles prepared in the embodiment 2, the obtained morphology is shown in the attached figure 2, and the obtained nanoparticles are uniform in size and have the particle size of 110-125 nm. BET analysis is carried out on the hollow calcium carbonate nanoparticles prepared in example 2, and as shown in figure 3, the specific surface area of the hollow calcium carbonate nanoparticles is 118-150 m2And/g, has a pore structure with the size of 3-20 nm. PXRD characterization was performed on the hollow calcium carbonate nanoparticles prepared in example 2, as shown in fig. 4, there is no obvious diffraction peak in PXRD spectrum, and only two broad peaks appear at 30 ° and 45 ° 2 θ, which is the characteristic peak position of amorphous calcium carbonate, indicating that the hollow calcium carbonate nanoparticles prepared are amorphous structure.
Example 3
Hollow calcium carbonate nanoparticles were prepared according to the procedure of example 1, with the final concentration of sodium citrate controlled at 5mM, and other process conditions unchanged. The particle size is 115-130 nm and the specific surface area is 112-138m2And/g, has a pore structure with the size of 5-18 nm.
Comparative examples 1 to 4
Calcium carbonate nanoparticles, which were measured to have particle sizes of about 46nm, 218nm and 255nm, were prepared according to the process of example 1 by controlling the final concentrations of sodium citrate at 0.625mM (comparative example 1), 10mM (comparative example 2) and 12.5mM (comparative example 3) without changing other process conditions. Wherein the calcium carbonate nanoparticles prepared in the comparative example 1 have no obvious hollow structure, and the hollow calcium carbonate nanoparticles prepared in the comparative examples 2 to 3 have obvious agglomeration growth phenomenon and poor dispersibility.
According to the process of example 1, the calcium carbonate nanoparticles were prepared without adding sodium citrate, i.e., at a final concentration of 0mM (comparative example 4), and other process conditions were not changed, and at 4h of reaction, only aggregates of a network-like cross-linked structure were obtained, and calcium carbonate nanoparticles having good sphericity could not be obtained, and TEM characterization results thereof are shown in fig. 5. Therefore, the control of the concentration of sodium citrate by the above examples 1 to 3 and comparative examples 1 to 4 shows that sodium citrate, as a calcium ion chelating agent, helps to accelerate the formation of calcium carbonate nanoparticles; secondly, the proper concentration (1.25-5 mM) of the sodium citrate is controlled, and the method plays an important role in regulating and controlling the dispersibility and the particle size of the hollow calcium carbonate nanoparticles.
Example 4
Adding calcium chloride dihydrate (CaCl)2·2H2O) and dopamine hydrochloride (Dop) in a mass ratio of 150: 4, dissolving in 50mL of absolute ethyl alcohol solution, and performing ultrasonic treatment at room temperature for 5min to uniformly mix; then, an appropriate amount of sodium citrate was added to give a final sodium citrate concentration of 2.5mM, and ultrasonic dispersion was carried out for 5min to obtain a clear mixed solution, which was placed in a beaker A with a seal of aluminum foil paper, leaving 40 small holes in the aluminum foil paper. At the same time, 2.5g of ammonium bicarbonate was loaded into the petri dish B and placed open. And (2) adjacently placing the beaker A and the culture dish B in a sealed jacket reactor, placing the reactor on a magnetic stirrer, controlling the reaction temperature to be 40 ℃, the stirring speed of the solution in the beaker A to be 200rpm, changing the solution into blue after the reaction time is 4 hours, centrifugally separating the obtained product at the rotating speed of 8000rpm, and washing the product with ethanol for three times to obtain the hollow calcium carbonate nanoparticles. The particle size of the material is 127-140 nm through measurement, and the material has a pore channel structure with the size of 10-25 nm.
Example 5
The preparation process according to example 4, wherein calcium chloride dihydrate (CaCl)2·2H2O) and dopamine hydrochloride (Dop) in a mass ratio of 150: 8 is dissolved in 50mL of absolute ethyl alcohol solution, and other conditions are unchanged to obtain the hollow calcium carbonate nano-particles. The particle size of the material is 129-154 nm through measurement, and the material has a pore channel structure with the size of 8-30 nm.
Comparative examples 5 to 6
Calcium chloride dihydrate (CaCl) was prepared according to the procedure of example 42·2H2O) and dopamine hydrochloride (Dop) are controlled in a mass ratio of 150: 16 (comparative example 5), the hollow calcium carbonate nanoparticles prepared under the unchanged other process conditions have larger particle size distribution of 145-330 nm, the size of the hollow structure of 5-56 nm and larger difference of the hollow structure, and are difficult to control to obtain uniform hollow-scale nanoparticles.
Calcium chloride dihydrate (CaCl) was prepared according to the procedure of example 42·2H2O) and dopamine hydrochloride (Dop) are controlled in a mass ratio of 150: 0 (comparative example 6), that is, Dop is not added in the reaction system, and other process conditions are not changed to prepare the calcium carbonate nanoparticles, the obtained calcium carbonate nanoparticles are solid-structure calcium carbonate nanoparticles without hollow structures, the particle size is 92-110 nm, and the TEM characterization result is shown in figure 6.
Through the regulation and control of the mass ratio of the calcium chloride dihydrate to the dopamine hydrochloride in the above examples 2, 4 and 5 and comparative examples 5 to 6, the fact that the dopamine hydrochloride has an important influence on the regulation and control of the formation of the hollow structure is shown, and the control of the mass ratio of the calcium chloride dihydrate to the dopamine hydrochloride is suitable, so that the controllable regulation of the hollow size of the calcium carbonate nanoparticles is facilitated.
Example 6
Adding calcium chloride dihydrate (CaCl)2·2H2O) and dopamine hydrochloride (Dop) in a mass ratio of 150: 2, dissolving in 250mL of absolute ethyl alcohol solution, and performing ultrasonic treatment at room temperature for 10min to uniformly mix; adding appropriate amount of sodium citrate to give final concentration of 2.5mM, ultrasonic dispersing for 10min to obtain clear mixed solution, placing the mixed solution in beaker A with aluminum foil paper seal, and leaving 10% on the aluminum foil paper0 holes. At the same time, 5.0g of ammonium bicarbonate was loaded into the petri dish B and placed open. And (2) placing the beaker A and the culture dish B in a sealed jacket reactor together in an adjacent manner, placing the reactor on a magnetic stirrer, controlling the reaction temperature to be 40 ℃, the stirring speed of the solution in the beaker A to be 300rpm, changing the solution into blue after the reaction time is 4 hours, centrifugally separating the obtained product at the rotating speed of 8000rpm, and washing the product with ethanol for three times to obtain the hollow nano calcium carbonate nanoparticles. The particle size is 106-128 nm and the specific surface area is 121-2And/g, has a pore structure with the size of 5-20 nm. Example 6 is a 5-fold volume amplification experiment of example 2, and the prepared hollow calcium carbonate nanoparticles have similar morphology and product performance, indicating that the method is helpful for realizing stable mass production of the hollow calcium carbonate nanoparticles.
Comparative example 7
According to the literature (Dong, Z.L.; Feng, L.Z.; Hao, Y., Synthesis of Hollow Biominerized CaCO)3Polydopamine Nanoparticles for Multimodal Imaging-Guided Cancer phosphor Therapy with Reduced Skin phosphor sensitivity, J.Am.chem.Soc.2018,140,2165-2178) reports dissolving 150mg of calcium chloride dihydrate and 1-4 mg of dopamine hydrochloride in 100mL of absolute ethanol, placing a beaker containing the above solution and a beaker containing 5g of ammonium bicarbonate in a vacuum drier, controlling the reaction temperature to 40 ℃, reacting for 24h, and centrifuging to obtain the hollow calcium carbonate Nanoparticles. The reaction rate of the hollow calcium carbonate nanoparticles prepared in the comparative example is slow, the synthesis period is long, generally more than 24 hours, and the stable and controllable hollow calcium carbonate nanoparticles are not easy to obtain quickly.
The above examples show that in the process of preparing the hollow calcium carbonate nanoparticles, a proper amount of sodium citrate is added as a calcium ion complexing agent and dopamine hydrochloride with a proper concentration, so that the shape and size of calcium carbonate can be synergistically regulated, the formation of the hollow amorphous calcium carbonate nanoparticles can be accelerated, the hollow calcium carbonate nanoparticles with good dispersibility can be rapidly prepared within a short time (2-4 hours), and the preparation efficiency of the nanoparticles is greatly improved. The obtained calcium carbonate nanoparticles are uniform in size, appropriate in hollow size and large in specific surface area, and have potential application in the fields of heavy metal ion adsorption and removal and the like besides being used as a high-efficiency drug carrier.
Claims (10)
1. A preparation method of double-additive mediated hollow calcium carbonate nanoparticles is characterized by comprising the following steps:
(1) dissolving a precursor calcium salt and dopamine hydrochloride in an alcohol solution, adding sodium citrate into the alcohol solution, and performing ultrasonic mixing to obtain a mixed solution;
(2) and placing the mixed solution in a container A sealed by aluminum foil paper with holes, placing the container A and a container B filled with ammonium bicarbonate in a sealed jacket reactor adjacently, reacting the reactor in a stirring manner until the mixed solution turns blue, taking out the mixed solution, and centrifuging and washing the mixed solution to obtain the hollow calcium carbonate nano-particles.
2. The dual-additive mediated hollow calcium carbonate nanoparticle preparation method according to claim 1, wherein the precursor calcium salt comprises any one of calcium chloride dihydrate, calcium nitrate, calcium acetate, calcium perchlorate; the alcohol solution comprises any one of ethanol, methanol, propanol and butanol.
3. The method for preparing hollow calcium carbonate nanoparticles mediated by double additives as claimed in claim 1, wherein in the step (1), the mass ratio of precursor calcium salt to dopamine hydrochloride is 150: (1-16);
the concentration of the precursor calcium salt in the mixed solution is 0.01-2 wt%;
the concentration of the dopamine hydrochloride in the mixed solution is 0.1-1 mM.
4. The dual-additive mediated preparation method of hollow calcium carbonate nanoparticles according to claim 1, wherein in the step (1), the concentration of sodium citrate in the mixed solution is not higher than 10 mM.
5. The method for preparing hollow calcium carbonate nanoparticles mediated by double additives as claimed in claim 1, wherein in the step (1), the concentration of sodium citrate in the mixed solution is 1.25-5 mM.
6. The method for preparing hollow calcium carbonate nanoparticles mediated by double additives as claimed in claim 1, wherein in the step (1), the ultrasonic power is 50-200W, the ultrasonic time is 3-15min, and the ultrasonic frequency is 20-60 KHz.
7. The method for preparing hollow calcium carbonate nanoparticles mediated by double additives as claimed in claim 1, wherein in the step (2), the mass-to-volume ratio of the ammonium bicarbonate to the mixed solution is 1-10g:50 mL.
8. The method for preparing hollow calcium carbonate nanoparticles mediated by double additives as claimed in claim 1, wherein in the step (2), the reaction temperature is 40-60 ℃ and the reaction time is 2-4 h;
the number of the openings of the aluminum foil paper is 30-100, and the aperture is 5-20 mm.
9. The method for preparing hollow calcium carbonate nanoparticles mediated by double additives as claimed in claim 1, wherein in the step (2), the centrifugation time is 5-20min, and the centrifugation speed is 4000-8000 rpm; washing with alcohol solution for 2-5 times.
10. The hollow calcium carbonate nanoparticle prepared by the preparation method according to any one of claims 1 to 9, wherein the hollow calcium carbonate nanoparticle has a particle size of 70 to 180nm and a specific surface area of 60 to 170m2And/g, has a pore structure with the size of 3-30 nm.
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