CN115196661A - Metal oxide or peroxide doped hollow calcium carbonate nanosphere and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a hollow calcium carbonate nanosphere doped with metal oxide or peroxide and a preparation method and application thereof, wherein amorphous calcium carbonate nanospheres are dispersed in a metal ion alcohol solution, and are stirred and then centrifuged to obtain the metal ion-doped amorphous calcium carbonate nanospheres; mixing alcohol suspension of the amorphous calcium carbonate nanospheres doped with the metal ions with aqueous solution of hydrogen peroxide, and centrifuging after reaction to obtain the hollow calcium carbonate nanospheres doped with the metal oxide or the peroxide. The method has the advantages of mild conditions, simple process and quick reaction, can conveniently regulate and control the type and content of the metal oxide in the calcium carbonate by changing the type and concentration of the metal ions, and has application prospect in various fields such as rubber, plastics, papermaking, printing ink, coating, daily chemical products, medicine and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to a hollow calcium carbonate nanosphere doped with metal oxide or peroxide, and a preparation method and application thereof.
Background
The nano calcium carbonate is widely used as a material for toughening, filling, oil absorption, whitening, sterilization and the like in the industries of rubber, plastics, papermaking, printing ink, coating, daily chemical products, medicines and the like, and is an industrial raw material with great potential. At present, the calcium carbonate material has the defects of single appearance and limited functions, and can not meet the requirement of the market on multifunctional micron/nanometer calcium carbonate. The functionalization of micro/nano calcium carbonate has become a development trend of the calcium carbonate industry. The metal ion doped micro/nano calcium carbonate is an important research direction of the functionalized calcium carbonate, and the calcium ions are partially replaced by the metal ions in the modes of lattice substitution and the like, so that the calcium carbonate can have the functions of fluorescence, magnetic resonance imaging and the like, and can be used in the fields of illumination, display, instruments, imaging detection and the like.
Different from the mature industrial production and application of calcium carbonate nanospheres, the research on metal-doped micro/nano calcium carbonate is usually in the initial stage, but the metal-doped micro/nano calcium carbonate with a special hollow structure is not reported.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide the hollow calcium carbonate nanosphere doped with the metal oxide or the peroxide, and the preparation method and the application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of metal oxide or peroxide doped hollow calcium carbonate nanospheres comprises the following steps:
(1) Dispersing the amorphous calcium carbonate nanospheres in a metal ion alcohol solution, stirring, and centrifuging to obtain metal ion-doped amorphous calcium carbonate nanospheres;
(2) Mixing alcohol suspension of the amorphous calcium carbonate nanospheres doped with the metal ions with aqueous solution of hydrogen peroxide, and centrifuging after reaction to obtain the hollow calcium carbonate nanospheres doped with the metal oxide or the peroxide.
The invention is further improved in that the amorphous calcium carbonate nanospheres described in step (1) are prepared by the following processes: and (2) placing the alcohol solution of calcium ions into a container with a plurality of air holes, then placing the container into a dryer filled with ammonium carbonate and/or ammonium bicarbonate, standing and reacting for 6 hours to 5 days at the temperature of between 20 and 50 ℃, and centrifuging to obtain the amorphous calcium carbonate nanospheres.
The further improvement of the invention is that the alcohol solution of calcium ions is a methanol, ethanol or propanol solution of calcium chloride, calcium chloride dihydrate, calcium nitrate or calcium nitrate tetrahydrate, and the concentration of the calcium ions in the alcohol solution is 0.2 millimole/liter-2 millimole/liter; the diameter of the amorphous calcium carbonate nanosphere is 10-1000 nanometers.
In a further improvement of the invention, the metal ion alcoholic solution in the step (1) is an alcoholic solution of chlorides or nitrates of magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, molybdenum, barium, silver, cadmium, barium, gold, platinum, and lanthanides.
The invention has the further improvement that the mass concentration of the amorphous calcium carbonate nanospheres in the step (1) in the metal ion alcohol solution is 1-50%, and the mass concentration of the metal ion alcohol solution is 0.1-10%.
The invention is further improved in that the mass concentration of the metal ion doped amorphous calcium carbonate nanosphere alcohol suspension in the step (2) is 0.1-50%, the mass concentration of the aqueous hydrogen peroxide solution is 5-80%, and the volume ratio of the alcohol suspension to the aqueous hydrogen peroxide solution is 1:9-9:1.
The invention is further improved in that the alcohol in the step (1) and the step (2) is methanol, ethanol or propanol, the centrifugal speed is 2000 rpm-20000 rpm, and the centrifugal time is 5 min-30 min.
The invention is further improved in that the stirring time in the step (1) is 5 minutes to 24 hours, and the reaction time in the step (2) is 5 minutes to 6 hours.
A metal oxide or peroxide doped hollow calcium carbonate nanosphere prepared according to the method as described above, which has a hollow spherical structure, an average particle diameter of 10 nm to 1000 nm, and a cavity diameter of 5 nm to 800 nm.
The application of the metal oxide or peroxide doped hollow calcium carbonate nanosphere in the fields of rubber, plastics, papermaking, ink, coating, daily chemical products or medicines.
The further improvement of the invention is the application of the metal oxide or peroxide doped hollow calcium carbonate nanospheres in preparing antitumor drugs.
The invention has the further improvement that the anti-tumor medicine is an anti-breast cancer medicine.
Compared with the prior art, the invention has the following beneficial effects:
the invention can prepare the nanosphere with a hollow structure by simply mixing the hydrogen peroxide and the amorphous calcium carbonate nanosphere doped with the metal ions, and can also dope the metal oxide or the peroxide on the pore wall of the calcium carbonate nanosphere, and the process has the advantages of simple flow, mild condition and quick reaction; because the hydrogen peroxide effectively regulates and controls the crystallization process of the amorphous calcium carbonate, the prepared hollow calcium carbonate nanosphere doped with the metal oxide or the peroxide has the advantages of good repeatability, uniform cavity aperture and good dispersibility; the type and content of the metal oxide in the calcium carbonate can be conveniently regulated and controlled by changing the type and concentration of the metal ions.
The hollow structure of the nanosphere prepared by the invention can obviously improve the adsorption capacity of the nanosphere and reduce the density of the nanosphere, and the metal oxide or peroxide can endow the nanosphere with abundant functions, so the hollow calcium carbonate nanosphere doped with the metal oxide or the peroxide has wide application prospect in various fields such as rubber, plastics, papermaking, printing ink, coating, daily chemical products, medicine and the like.
Drawings
Fig. 1 is a transmission electron micrograph of the synthesized amorphous calcium carbonate nanosphere of example 1;
fig. 2 is a transmission electron micrograph and a scanning transmission electron micrograph of the copper peroxide-doped hollow calcium carbonate nanospheres synthesized in example 1; wherein A is a transmission electron microscope photograph, and B is a scanning transmission electron microscope photograph;
fig. 3 is an element distribution diagram of the copper peroxide doped hollow calcium carbonate nanospheres synthesized in example 1.
FIG. 4 is a confocal microscope photograph of 4T1 cells after the doxorubicin-loaded copper peroxide doped hollow calcium carbonate nanospheres synthesized in example 1 are co-cultured with mouse breast cancer 4T1 cells for 24 hours; wherein (a) represents the distribution of nuclei (Hoechst), (b) represents the distribution of Doxorubicin (DOX), and (c) is a fusion picture (merge).
Detailed Description
The present invention will be further illustrated by reference to specific examples, which are intended to illustrate the invention and not to limit the scope thereof, and it will be apparent that the examples are given by way of illustration only and are not intended to limit the scope thereof.
The calcium carbonate material with the hollow structure has the remarkable advantages of low density, good permeability, large specific surface area, high adsorption rate and the like, has good application potential in the fields of biological medicines, daily chemical products, adsorption separation and the like, can endow calcium carbonate with richer functions and wider application scenes through metal doping and morphology regulation, and remarkably improves the performance and the additional value of the calcium carbonate.
The invention discloses a preparation method of metal oxide or peroxide doped hollow calcium carbonate nanospheres, which comprises the following steps of:
(1) And (2) placing the alcohol solution of calcium ions into a container with a plurality of air holes, then placing the container into a dryer filled with ammonium carbonate and/or ammonium bicarbonate, standing and reacting for 6 hours to 5 days at the temperature of between 20 and 50 ℃, and centrifuging the reaction solution to obtain the amorphous calcium carbonate nanospheres. The total mass of ammonium carbonate and/or ammonium bicarbonate is 1 to 30 grams when the alcoholic solution of calcium ions is 50 to 500 milliliters;
wherein the alcohol solution of calcium ions is a methanol, ethanol or propanol solution of calcium chloride, calcium chloride dihydrate, calcium nitrate or calcium nitrate tetrahydrate, the concentration of the calcium ions in the alcohol solution is 0.2 mmol/L-2 mol/L, and the total mass of ammonium carbonate and/or ammonium bicarbonate is 1 g-30 g. When the concentration of calcium ions in the alcohol solution is small, the particle size of the prepared nanospheres is small, and when the concentration is large, the particle size of the prepared nanospheres is large.
The diameter of the amorphous calcium carbonate nanosphere is 10-1000 nanometers.
(2) Dispersing the amorphous calcium carbonate nanospheres in an alcohol solution of metal ions, stirring for 5 minutes to 24 hours, and centrifuging to obtain the metal ion-doped amorphous calcium carbonate nanospheres.
Wherein the metal ion solution is methanol, ethanol or propanol solution of chloride or nitrate of magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, molybdenum, barium, silver, cadmium, barium, gold, platinum or lanthanide.
The mass concentration of the amorphous calcium carbonate nanospheres in the metal ion alcoholic solution is 1-50%, and the mass concentration of the metal ion alcoholic solution is 0.1-10%.
(3) Mixing alcohol suspension of the metal ion doped amorphous calcium carbonate nanospheres with aqueous solution of hydrogen peroxide, reacting for 5 minutes to 6 hours, and centrifuging to obtain the metal oxide or peroxide doped hollow calcium carbonate nanospheres.
Wherein the mass concentration of the metal ion doped amorphous calcium carbonate nanosphere alcohol suspension is 0.1-50%, the mass concentration of the hydrogen peroxide aqueous solution is 5-80%, and the volume ratio of the alcohol suspension to the hydrogen peroxide aqueous solution is 1:9-9:1.
The alcohol in the steps (1), (2) and (3) is methanol, ethanol or propanol, the centrifugal rotating speed is 2000 rpm-20000 rpm, and the centrifugal time is 5 minutes-30 minutes.
The metal oxide or peroxide doped calcium carbonate nanospheres obtained by the method have a hollow spherical structure, the average particle size is 10-1000 nanometers, the diameter of a cavity is 5-800 nanometers, the dispersibility is good, and the metal oxide or peroxide doped calcium carbonate nanospheres can be used in the fields of rubber, plastics, papermaking, printing ink, coatings, daily chemical products, medicines and the like, and can be particularly applied to preparation of antitumor drugs.
The following are specific examples.
Example 1
(1) 100 ml of ethanol solution of calcium chloride dihydrate with the concentration of 0.01 mol/L is placed in a container with a plurality of air holes, then the container is placed in a drier filled with 10 g of ammonium bicarbonate, the mixture is kept stand at 40 ℃ for 24 hours for reaction, and the mixture is centrifuged at 10000 r/min for 10 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into an ethanol solution of copper chloride with the mass concentration of 2% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 20%, stirring for 30 minutes, and centrifuging at 10000 rpm for 10 minutes to obtain the copper ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of the copper ion doped amorphous calcium carbonate nanosphere with the mass concentration of 1% and 30 ml of aqueous hydrogen peroxide solution with the mass concentration of 30%, reacting for 30 minutes, and centrifuging at 10000 r/min for 10 minutes to obtain the copper peroxide doped hollow calcium carbonate nanosphere.
As can be seen from FIG. 1, the prepared amorphous calcium carbonate is spherical, has good dispersibility and has a particle size of about 100 nm.
As can be seen from A and B in FIG. 2, the prepared copper peroxide doped calcium carbonate nanospheres have a spherical hollow structure, good dispersibility, a particle size of about 100 nm and a cavity diameter of about 70 nm.
As can be seen from fig. 3 (a), (b), (c), (d) and (e), the elements carbon, calcium, oxygen and copper are uniformly distributed in the nanosphere, indicating that the copper peroxide doped hollow calcium carbonate nanosphere is successfully prepared.
The effect of delivering anticancer drugs to cancer cells by the copper peroxide doped hollow calcium carbonate nanospheres was evaluated using Doxorubicin (DOX) as a model drug. First, a 10 mg/ml solution of DOX in ethanol was prepared as in example 1And uniformly mixing the ethanol suspension of the copper peroxide doped hollow calcium carbonate nanospheres, stirring for 1 hour, and centrifuging to obtain DOX-loaded hollow calcium carbonate nanospheres doped with copper peroxide. Subsequently, the ability of the copper peroxide-doped hollow calcium carbonate nanospheres to deliver DOX into mouse breast cancer 4T1 cells was evaluated using confocal laser microscopy. 4T1 cells were plated at 1X 10 5 The density of individual cells/dish was seeded on a confocal laser culture dish. After 24 hours of regular incubation, nanospheres were added to the dish and incubation was continued for 24 hours. The nuclei were then stained with Hoechst and cellular uptake of DOX was observed under a confocal laser microscope.
As can be seen from (a), (b) and (c) in fig. 4, mouse breast cancer 4T1 cells can effectively take up DOX, which indicates that the copper peroxide doped hollow calcium carbonate nanospheres can deliver DOX into cancer cells, proving that it can be used for preparing anti-breast cancer drugs, and has application potential in the field of tumor therapy.
Example 2
(1) 100 ml of ethanol solution of calcium chloride dihydrate with the concentration of 0.1 mol/L is placed in a container with a plurality of air holes, then the container is placed in a drier with 20 g of ammonium bicarbonate, the mixture is kept still at 40 ℃ for 24 hours to react, and the mixture is centrifuged at 8000 rpm for 10 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into a methanol solution of copper chloride with the mass concentration of 1% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 30%, stirring for 30 minutes, and centrifuging at 8000 rpm for 10 minutes to obtain the copper ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of methanol suspension of the copper ion doped amorphous calcium carbonate nanosphere with the mass concentration of 1% with 30 ml of aqueous hydrogen peroxide solution with the mass concentration of 30%, reacting for 30 minutes, and centrifuging at 10000 r/min for 10 minutes to obtain the copper peroxide doped hollow calcium carbonate nanosphere.
Example 3
(1) 50 ml of 0.01 mol/L ethanol solution of calcium chloride dihydrate is placed in a container with a plurality of air holes, then the container is placed in a drier with 10 g of ammonium carbonate, is kept stand at 40 ℃ for 24 hours for reaction, and is centrifuged at 10000 rpm for 10 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into an ethanol solution of ferrous chloride with the mass concentration of 2% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 20%, stirring for 30 minutes, and centrifuging at 10000 rpm for 10 minutes to obtain the copper ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of the ferrous ion doped amorphous calcium carbonate nanosphere with the mass concentration of 1% and 50 ml of aqueous hydrogen peroxide with the mass concentration of 30%, reacting for 30 minutes, and centrifuging at 10000 r/min for 10 minutes to obtain the ferric oxide doped hollow calcium carbonate nanosphere.
Example 4
(1) 500 ml of 0.01 mol/L calcium nitrate methanol solution is placed in a container with a plurality of air holes, then the container is placed in a drier with 20 g of ammonium carbonate, the mixture is kept still at 50 ℃ for 12 hours and centrifuged at 5000 r/min for 20 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into an ethanol solution of manganese chloride with the mass concentration of 2% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 20%, stirring for 30 minutes, and centrifuging at 5000 rpm for 20 minutes to obtain the manganese ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of the manganese ion doped amorphous calcium carbonate nanosphere with the mass concentration of 1% with 60 ml of aqueous hydrogen peroxide with the mass concentration of 30%, reacting for 30 minutes, and centrifuging at 5000 r/min for 20 minutes to obtain the manganese oxide doped hollow calcium carbonate nanosphere.
Example 5
(1) 200 ml of ethanol solution of calcium nitrate tetrahydrate with the concentration of 0.1 mol/L is placed in a container with a plurality of air holes, then the container is placed in a drier filled with 15 g of ammonium bicarbonate, the mixture is kept stand at 40 ℃ for reaction for 48 hours, and the mixture is centrifuged at 8000 rpm for 10 minutes to obtain amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into a gadolinium chloride ethanol solution with the mass concentration of 3% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 20%, stirring for 30 minutes, and centrifuging at 8000 rpm for 10 minutes to obtain gadolinium ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of the gadolinium ion doped amorphous calcium carbonate nanospheres with the mass concentration of 2% with 60 ml of 20% aqueous hydrogen peroxide solution, reacting for 1 hour, and centrifuging at 8000 rpm for 10 minutes to obtain the gadolinium oxide doped hollow calcium carbonate nanospheres.
Example 6
(1) 300 ml of ethanol solution of calcium nitrate tetrahydrate with the concentration of 0.2 mol/L is placed in a container with a plurality of air holes, then the container is placed in a drier filled with 15 g of ammonium bicarbonate, the mixture is kept still at 40 ℃ for reaction for 48 hours, and the mixture is centrifuged at 8000 rpm for 10 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into an ethanol solution of europium chloride with the mass concentration of 3% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 20%, stirring for 30 minutes, and centrifuging at 8000 rpm for 10 minutes to obtain the europium ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of the europium ion doped amorphous calcium carbonate nanosphere with the mass concentration of 2% with 60 ml of 20% aqueous hydrogen peroxide solution, reacting for 1 hour, and centrifuging at 8000 rpm for 10 minutes to obtain the europium oxide doped hollow calcium carbonate nanosphere.
Example 7
(1) 400 ml of 0.2 mol/L calcium chloride ethanol solution is placed in a container with a plurality of air holes, then the container is placed in a drier with 15 g of ammonium bicarbonate, the mixture is kept still at 40 ℃ for reaction for 48 hours, and the mixture is centrifuged at 8000 rpm for 10 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into an ethanol solution of titanium chloride with the mass concentration of 3% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 20%, stirring for 30 minutes, and centrifuging at 8000 rpm for 10 minutes to obtain the titanium ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of the titanium ion doped amorphous calcium carbonate nanosphere with the mass concentration of 2% and 60 ml of aqueous hydrogen peroxide with the mass concentration of 20%, reacting for 1 hour, and centrifuging at 8000 rpm for 10 minutes to obtain the titanium dioxide doped hollow calcium carbonate nanosphere.
Example 8
(1) 100 ml of 0.05 mol/L calcium chloride propanol solution is placed in a container with a plurality of air holes, then the container is placed in a dryer with 1 g of ammonium bicarbonate and ammonium carbonate (the total mass of the ammonium bicarbonate and the ammonium carbonate is 1 g), standing reaction is carried out for 6 hours at 20 ℃, and the amorphous calcium carbonate nanospheres are obtained by centrifugation at 2000 r/min for 30 minutes.
(2) Dispersing the amorphous calcium carbonate nanospheres into a propanol solution of aluminum chloride with the mass concentration of 0.1% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 50%, stirring for 5 minutes, and centrifuging at 2000 rpm for 30 minutes to obtain aluminum ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of the aluminum ion doped amorphous calcium carbonate nanosphere with the mass concentration of 0.1% and 90 ml of aqueous hydrogen peroxide with the mass concentration of 5%, reacting for 5 minutes, and centrifuging at 2000 rpm for 30 minutes to obtain the aluminum oxide doped hollow calcium carbonate nanosphere.
Example 9
(1) 50 ml of ethanol solution of calcium chloride with the concentration of 0.5 mol/L is placed in a container with a plurality of air holes, then the container is placed in a drier filled with 5 g of ammonium bicarbonate, the mixture is kept still at 30 ℃ for reaction for 20 hours, and the mixture is centrifuged at 4000 rpm for 25 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into an ethanol solution of nickel nitrate with the mass concentration of 10% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 1%, stirring for 60 minutes, and centrifuging at 4000 rpm for 25 minutes to obtain nickel ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of the nickel ion doped amorphous calcium carbonate nanosphere with the mass concentration of 50% with 10 ml of aqueous hydrogen peroxide with the mass concentration of 80%, reacting for 40 minutes, and centrifuging at 4000 revolutions per minute for 25 minutes to obtain the nickel oxide doped hollow calcium carbonate nanosphere.
Example 10
(1) Placing 80 ml of ethanol solution of calcium chloride with the concentration of 0.2 mmol/L into a container with a plurality of air holes, then placing the container into a drier containing 12 g of ammonium bicarbonate, standing at 40 ℃ for reaction for 36 hours, and centrifuging at 8000 rpm for 20 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into an ethanol solution of lanthanum nitrate with the mass concentration of 10% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 10%, stirring for 5 hours, and centrifuging at 8000 rpm for 20 minutes to obtain the lanthanum ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of the lanthanum ion doped amorphous calcium carbonate nanosphere with the mass concentration of 7% and 5 ml of hydrogen peroxide water solution with the mass concentration of 60%, reacting for 2 hours, and centrifuging at 8000 rpm for 20 minutes to obtain the lanthanum oxide doped hollow calcium carbonate nanosphere.
Example 11
(1) 150 ml of ethanol solution of calcium chloride with the concentration of 1 mmol/L is placed in a container with a plurality of air holes, then the container is placed in a drier with 25 g of ammonium bicarbonate, the mixture is kept still at 50 ℃ for reaction for 120 hours, and the mixture is centrifuged at 13000 rpm for 10 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into a 5% cerium chloride ethanol solution to obtain a 30% amorphous calcium carbonate nanosphere suspension, stirring for 24 hours, and centrifuging at 13000 r/min for 10 minutes to obtain the actinium oxide ion doped amorphous calcium carbonate nanospheres.
(3) Mixing 9 ml of ethanol suspension of the cerium ion doped amorphous calcium carbonate nanosphere with the mass concentration of 15% and 1 ml of aqueous hydrogen peroxide with the mass concentration of 50%, reacting for 3 hours, and centrifuging at 13000 r/min for 10 minutes to obtain the cerium oxide doped hollow calcium carbonate nanosphere.
Example 12
(1) 200 ml of ethanol solution of calcium chloride with the concentration of 1 mol/L is placed in a container with a plurality of air holes, then the container is placed in a drier filled with 30 g of ammonium bicarbonate, the mixture is kept still at 25 ℃ for reaction for 80 hours, and the mixture is centrifuged at 15000 r/min for 10 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into an ethanol solution of titanium chloride with the mass concentration of 8% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 40%, stirring for 16 hours, and centrifuging at 15000 r/min for 10 minutes to obtain the titanium ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 9 ml of ethanol suspension of the titanium ion doped amorphous calcium carbonate nanosphere with the mass concentration of 30% and 4 ml of aqueous hydrogen peroxide with the mass concentration of 40%, reacting for 4 hours, and centrifuging at 15000 r/min for 10 minutes to obtain the titanium dioxide doped hollow calcium carbonate nanosphere.
Example 13
(1) 100 ml of 2 mol/L calcium chloride ethanol solution is placed in a container with a plurality of air holes, then the container is placed in a drier filled with 10 g of ammonium bicarbonate, the mixture is kept still at 35 ℃ for reaction for 60 hours, and is centrifuged at 20000 r/min for 5 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into an ethanol solution of titanium chloride with the mass concentration of 6% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 25%, stirring for 10 hours, and centrifuging at 20000 rpm for 5 minutes to obtain the titanium ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 9 ml of ethanol suspension of the titanium ion doped amorphous calcium carbonate nanosphere with the mass concentration of 40% and 7 ml of hydrogen peroxide water solution with the mass concentration of 30%, reacting for 6 hours, and centrifuging at 20000 revolutions per minute for 5 minutes to obtain the titanium dioxide doped hollow calcium carbonate nanosphere.
Example 14
(1) 250 ml of 0.2 mol/L calcium chloride ethanol solution is placed in a container with a plurality of air holes, then the container is placed in a drier with 15 g of ammonium bicarbonate, the mixture is kept still at 40 ℃ for reaction for 48 hours, and the mixture is centrifuged at 8000 rpm for 10 minutes to obtain the amorphous calcium carbonate nanospheres.
(2) Dispersing the amorphous calcium carbonate nanospheres into an ethanol solution of titanium chloride with the mass concentration of 3% to obtain an amorphous calcium carbonate nanosphere suspension with the mass concentration of 20%, stirring for 30 minutes, and centrifuging at 8000 rpm for 10 minutes to obtain titanium ion-doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of the titanium ion doped amorphous calcium carbonate nanosphere with the mass concentration of 2% and 60 ml of aqueous hydrogen peroxide with the mass concentration of 20%, reacting for 1 hour, and centrifuging at 8000 rpm for 10 minutes to obtain the titanium dioxide doped hollow calcium carbonate nanosphere.
The metal ion solution in the invention adopts methanol, ethanol or propanol solution of chloride or nitrate of magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, molybdenum, barium, silver, cadmium, barium, gold, platinum and lanthanide elements, so as to realize the preparation of the hollow calcium carbonate nanosphere doped with metal oxide or peroxide.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and extensions, such as metal ion sources, can be made, and these improvements and extensions should also be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of hollow calcium carbonate nanospheres doped with metal oxide or peroxide is characterized by comprising the following steps:
(1) Dispersing the amorphous calcium carbonate nanospheres in a metal ion alcohol solution, stirring, and centrifuging to obtain metal ion-doped amorphous calcium carbonate nanospheres;
(2) Mixing alcohol suspension of the amorphous calcium carbonate nanospheres doped with the metal ions with aqueous solution of hydrogen peroxide, and centrifuging after reaction to obtain the hollow calcium carbonate nanospheres doped with the metal oxide or the peroxide.
2. The method for preparing metal oxide or peroxide doped hollow calcium carbonate nanospheres according to claim 1, wherein the amorphous calcium carbonate nanospheres of step (1) are prepared by the following process: and (2) placing the alcohol solution of calcium ions into a container with a plurality of air holes, then placing the container into a dryer filled with ammonium carbonate and/or ammonium bicarbonate, standing and reacting for 6 hours to 5 days at the temperature of between 20 and 50 ℃, and centrifuging to obtain the amorphous calcium carbonate nanospheres.
3. The method for preparing metal oxide or peroxide doped hollow calcium carbonate nanospheres according to claim 2, wherein the alcohol solution of calcium ions is a methanol, ethanol or propanol solution of calcium chloride, calcium chloride dihydrate, calcium nitrate or calcium nitrate tetrahydrate, and the concentration of calcium ions in the alcohol solution is 0.2 mmol/l to 2 mol/l; the diameter of the amorphous calcium carbonate nanosphere is 10-1000 nanometers.
4. The method for preparing metal oxide or peroxide doped hollow calcium carbonate nanospheres according to claim 1, wherein the metal ion alcoholic solution in step (1) is a methanol, ethanol or propanol solution of chloride or nitrate of magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, molybdenum, barium, silver, cadmium, barium, gold, platinum, lanthanide.
5. The method for preparing metal oxide or peroxide doped hollow calcium carbonate nanospheres according to claim 1, wherein the mass concentration of the amorphous calcium carbonate nanospheres in the metal ion alcohol solution in step (1) is 1-50%, and the mass concentration of the metal ion alcohol solution is 0.1-10%.
6. The method for preparing metal oxide or peroxide doped hollow calcium carbonate nanospheres according to claim 1, wherein the mass concentration of the alcohol suspension of the metal ion doped amorphous calcium carbonate nanospheres in step (2) is 0.1-50%, the mass concentration of the aqueous solution of hydrogen peroxide is 5-80%, and the volume ratio of the alcohol suspension to the aqueous solution of hydrogen peroxide is 1:9-9:1.
7. The method for preparing metal oxide or peroxide doped hollow calcium carbonate nanospheres according to claim 1, wherein the alcohol in step (1) and step (2) is methanol, ethanol or propanol, the centrifugation speed is 2000 rpm to 20000 rpm, and the centrifugation time is 5 minutes to 30 minutes.
8. The method for preparing metal oxide or peroxide doped hollow calcium carbonate nanospheres according to claim 1, wherein the stirring time in step (1) is 5 minutes to 24 hours, and the reaction time in step (2) is 5 minutes to 6 hours.
9. A metal oxide or peroxide doped hollow calcium carbonate nanosphere prepared according to the method of any of claims 1-8, wherein the hollow calcium carbonate nanosphere has a hollow spherical structure with an average particle size of 10 nm to 1000 nm and a cavity diameter of 5 nm to 800 nm.
10. Use of the metal oxide or peroxide doped hollow calcium carbonate nanospheres of claim 9 in the rubber, plastic, paper, ink, coating, commodity or medical field.
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| CN116350791A (en) * | 2023-03-13 | 2023-06-30 | 清华大学 | Universal preparation method for increasing drug loading rate by using ACC-entrapped metal ions |
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