CN115196661B - 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 metal oxide or peroxide doped hollow calcium carbonate nanosphere, a preparation method and application thereof, wherein amorphous calcium carbonate nanospheres are dispersed in a metal ion alcohol solution, stirred and centrifuged to obtain the metal ion doped amorphous calcium carbonate nanospheres; mixing the alcohol suspension of the amorphous calcium carbonate nanospheres doped with metal ions with the aqueous solution of hydrogen peroxide, and centrifuging after the reaction to obtain the metal oxide or peroxide doped hollow calcium carbonate nanospheres. The method has the advantages of mild conditions, simple flow and quick reaction, can conveniently regulate 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 prospects in various fields of rubber, plastics, paper making, printing ink, coating, daily chemicals, medicines and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to a metal oxide or peroxide doped hollow calcium carbonate nanosphere, 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, plastic, papermaking, printing ink, coating, daily chemical products, medicines and the like, and is an industrial raw material with great potential. The existing calcium carbonate material has the defects of single shape and limited functions, and can not meet the demands of the market on multifunctional micro/nano calcium carbonate. Functionalization of micro/nano calcium carbonate has become a trend in the calcium carbonate industry. The metal ion doped micro/nano calcium carbonate is an important research direction of functional calcium carbonate, and the metal ion is partially substituted for the calcium ion by adopting modes such as lattice substitution and the like, so that the calcium carbonate can be endowed with functions such as fluorescence luminescence, magnetic resonance imaging and the like, and can be used in the fields such as illumination, display, instruments and meters, imaging detection and the like.
Unlike the mature industrial production and application of calcium carbonate nanospheres, the research of metal doped micro/nano calcium carbonate is always in the starting stage, and the research of 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 a metal oxide or peroxide doped hollow calcium carbonate nanosphere, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a metal oxide or peroxide doped hollow calcium carbonate nanosphere comprises the following steps:
(1) Dispersing amorphous calcium carbonate nanospheres in a metal ion alcohol solution, stirring, and centrifuging to obtain metal ion doped amorphous calcium carbonate nanospheres;
(2) Mixing the alcohol suspension of the amorphous calcium carbonate nanospheres doped with metal ions with the aqueous solution of hydrogen peroxide, and centrifuging after the reaction to obtain the metal oxide or peroxide doped hollow calcium carbonate nanospheres.
The invention is further improved in that the amorphous calcium carbonate nanospheres described in step (1) are prepared by the following process: placing the alcoholic 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 at 20-50 ℃ for reaction for 6-5 days, and centrifuging to obtain the amorphous calcium carbonate nanospheres.
The invention is further improved in that the alcohol solution of calcium ions is 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 mmol/L-2 mol/L; the diameter of the amorphous calcium carbonate nanospheres is 10-1000 nanometers.
The invention is further improved in that 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, lanthanoid.
The invention is further improved in that the mass concentration of the amorphous calcium carbonate nanospheres in the step (1) in the metal ion alcoholic solution is 1% -50%, and the mass concentration of the metal ion alcoholic 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 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 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 2000-20000 revolutions per minute, and the centrifugal time is 5-30 minutes.
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, having a hollow spherical structure with 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 nanospheres in rubber, plastics, papermaking, printing ink, coating, daily chemical products or medicine fields.
The invention further improves the application of the metal oxide or peroxide doped hollow calcium carbonate nanospheres in preparing antitumor drugs.
The invention further improves that the anti-tumor drug is an anti-breast cancer drug.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, by simply mixing hydrogen peroxide and the metal ion doped amorphous calcium carbonate nanospheres, nanospheres with hollow structures can be prepared, and metal oxides or peroxides can be doped on the pore walls of the calcium carbonate nanospheres at the same time; because hydrogen peroxide effectively regulates and controls the crystallization process of amorphous calcium carbonate, the prepared metal oxide or peroxide doped hollow calcium carbonate nanospheres have the advantages of good repeatability, uniform cavity aperture and good dispersibility; the type and the concentration of metal ions can be changed to conveniently regulate the type and the content of metal oxides in the calcium carbonate.
The hollow structure of the nanosphere prepared by the invention can obviously improve the adsorption capacity and reduce the density of the nanosphere, and the metal oxide or the peroxide can endow the nanosphere with rich functions, so that the hollow calcium carbonate nanosphere doped with the metal oxide or the peroxide has wide application prospects in various fields such as rubber, plastics, papermaking, printing ink, coating, daily chemicals, medicines and the like.
Drawings
FIG. 1 is a transmission electron micrograph of amorphous calcium carbonate nanospheres synthesized in 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 photo, and B is a scanning transmission electron microscope photo;
FIG. 3 is an elemental distribution diagram of copper peroxide doped hollow calcium carbonate nanospheres synthesized in example 1.
FIG. 4 is a confocal laser microscope image of 4T1 cells after 24 hours of co-culture with 4T1 cells of mouse breast cancer after doxorubicin loading of hollow calcium carbonate nanospheres doped with copper peroxide synthesized in example 1; wherein, (a) represents the distribution of nuclei (Hoechst), (b) represents the distribution of Doxorubicin (DOX), and (c) is a fused picture (mered).
Detailed Description
The present invention will be further illustrated below in conjunction with specific embodiments, it being evident that the embodiments described are only a part of the present invention and not all embodiments of the present invention, the described embodiments being intended to illustrate the present invention and not to limit the scope of the present invention.
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 medicine, daily chemicals, adsorption separation and the like, can endow the calcium carbonate with richer functions and wider application scenes through metal doping and morphology regulation, and remarkably improves the performance and the added value of the calcium carbonate.
The invention relates to a preparation method of a metal oxide or peroxide doped hollow calcium carbonate nanosphere, which comprises the following steps:
(1) Placing the alcoholic 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 at 20-50 ℃ for reaction for 6-5 days, and centrifuging the reaction solution to obtain the amorphous calcium carbonate nanospheres. When the alcohol solution of calcium ions is 50-500 ml, the total mass of ammonium carbonate and/or ammonium bicarbonate is 1-30 g;
wherein the alcohol solution of calcium ions is 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. The concentration of calcium ions in the alcohol solution is small, the particle size of the prepared nanospheres is small, and the particle size of the prepared nanospheres is large when the concentration is large.
The diameter of the amorphous calcium carbonate nanospheres 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 amorphous calcium carbonate nanospheres doped with the metal ions.
Wherein the metal ion solution is a methanol, ethanol or propanol 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, lanthanoid.
The mass concentration of the amorphous calcium carbonate nanospheres in the metal ion alcohol solution is 1% -50%, and the mass concentration of the metal ion alcohol solution is 0.1% -10%.
(3) Mixing the alcohol suspension of the amorphous calcium carbonate nanospheres doped with metal ions with the aqueous solution of hydrogen peroxide, reacting for 5 minutes to 6 hours, and centrifuging to obtain the hollow calcium carbonate nanospheres doped with metal oxides or peroxides.
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 speed is 2000-20000 rpm, and the centrifugal time is 5-30 minutes.
The metal oxide or peroxide doped calcium carbonate nanospheres obtained by the method have a hollow spherical structure, an average particle diameter of 10-1000 nanometers, a cavity diameter of 5-800 nanometers and good dispersibility, can be used in the fields of rubber, plastics, papermaking, printing ink, paint, daily chemicals, medicines and the like, and can be particularly applied to the preparation of antitumor drugs.
The following are specific examples.
Example 1
(1) 100 milliliters 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 dryer filled with 10 grams of ammonium bicarbonate, the mixture is kept stand at 40 ℃ for reaction for 24 hours, and the amorphous calcium carbonate nanospheres are obtained by centrifugation at 10000 revolutions per minute for 10 minutes.
(2) Dispersing the amorphous calcium carbonate nanospheres in 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 for 10 minutes at 10000 revolutions per minute to obtain the copper ion doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of copper ion doped amorphous calcium carbonate nanospheres with mass concentration of 1% and 30 ml of hydrogen peroxide water solution with mass concentration of 30%, reacting for 30 minutes, and centrifuging for 10 minutes at 10000 revolutions per minute to obtain copper peroxide doped hollow calcium carbonate nanospheres.
As can be seen from FIG. 1, the amorphous calcium carbonate prepared is spherical, has good dispersibility and has a particle size of about 100 nanometers.
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 nanometers and a cavity diameter of about 70 nanometers.
As can be seen from fig. 3 (a), (b), (c), (d) and (e), the elemental carbon, calcium, oxygen and copper are uniformly distributed in the nanospheres, indicating successful preparation of copper peroxide doped hollow calcium carbonate nanospheres.
The effect of copper peroxide doped hollow calcium carbonate nanospheres on delivering anticancer drugs to cancer cells was evaluated using Doxorubicin (DOX) as a model drug. First, 10 mg/ml of DOX ethanol solution was mixed with the copper peroxide-doped hollow calcium carbonate nanosphere ethanol suspension prepared in example 1, stirred for 1 hour, and centrifuged to obtain DOX-loaded copper peroxide-doped hollow calcium carbonate nanospheres. Subsequently, the ability of copper peroxide doped hollow calcium carbonate nanospheres to deliver DOX into mouse breast cancer 4T1 cells was evaluated using a laser confocal microscope. 4T1 cells were grown at 1X 10 5 The density of individual cells/dish was seeded onto confocal laser dishes. After conventional incubation for 24 hours, nanospheres were added to the dish for further incubation for 24 hours. The nuclei were then stained with Hoechst and the uptake of DOX by the cells was observed under a laser confocal microscope.
From fig. 4 (a), (b) and (c), it can be seen that the mouse breast cancer 4T1 cells can effectively absorb DOX, which means that the copper peroxide doped hollow calcium carbonate nanospheres can deliver DOX into cancer cells, and prove that the copper peroxide doped hollow calcium carbonate nanospheres can be used for preparing anti-breast cancer drugs and have application potential in the tumor treatment field.
Example 2
(1) 100 milliliters 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 dryer filled with 20 grams of ammonium bicarbonate, the mixture is kept stand at 40 ℃ for reaction for 24 hours, and the amorphous calcium carbonate nanospheres are obtained after centrifugation at 8000 revolutions per minute for 10 minutes.
(2) Dispersing the amorphous calcium carbonate nanospheres in 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 for 10 minutes at 8000 rpm to obtain the copper ion doped amorphous calcium carbonate nanospheres.
(3) 10 ml of methanol suspension of copper ion doped amorphous calcium carbonate nanospheres with mass concentration of 1% and 30 ml of hydrogen peroxide water solution with mass concentration of 30% are mixed and reacted for 30 minutes, and 10000 revolutions per minute are centrifuged for 10 minutes to obtain copper peroxide doped hollow calcium carbonate nanospheres.
Example 3
(1) 50 milliliters 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 with 10 grams of ammonium carbonate, and the mixture is kept stand at 40 ℃ for reaction for 24 hours, and is centrifuged at 10000 revolutions per minute for 10 minutes to obtain amorphous calcium carbonate nanospheres.
(2) Dispersing amorphous calcium carbonate nanospheres in an ethanol solution of ferrous chloride with the mass concentration of 2% to obtain amorphous calcium carbonate nanosphere suspension with the mass concentration of 20%, stirring for 30 minutes, and centrifuging for 10 minutes at 10000 revolutions per minute 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 nanospheres with the mass concentration of 1% and 50 ml of hydrogen peroxide water solution with the mass concentration of 30%, reacting for 30 minutes, and centrifuging for 10 minutes at 10000 revolutions per minute to obtain the ferric oxide doped hollow calcium carbonate nanospheres.
Example 4
(1) 500 ml of a methanol solution of calcium nitrate 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 dryer with 20 g of ammonium carbonate, the mixture is kept stand at 50 ℃ for reaction for 12 hours, and the amorphous calcium carbonate nanospheres are obtained by centrifugation at 5000 rpm for 20 minutes.
(2) Dispersing the amorphous calcium carbonate nanospheres in 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 for 20 minutes at 5000 rpm to obtain the manganese ion doped amorphous calcium carbonate nanospheres.
(3) 10 ml of ethanol suspension of manganese ion doped amorphous calcium carbonate nanospheres with mass concentration of 1% and 60 ml of hydrogen peroxide water solution with mass concentration of 30% are mixed and reacted for 30 minutes, and the manganese oxide doped hollow calcium carbonate nanospheres are obtained after centrifugation for 20 minutes at 5000 revolutions per minute.
Example 5
(1) 200 milliliters of ethanol solution of tetrahydrate calcium nitrate 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 dryer filled with 15 grams 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 in an ethanol solution of gadolinium 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 for 10 minutes at 8000 rpm to obtain the gadolinium ion doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of gadolinium ion doped amorphous calcium carbonate nanospheres with the mass concentration of 2% and 60 ml of hydrogen peroxide water solution with the mass concentration of 20%, reacting for 1 hour, centrifuging at 8000 revolutions per minute for 10 minutes, and obtaining gadolinium oxide doped hollow calcium carbonate nanospheres.
Example 6
(1) 300 milliliters of ethanol solution of tetrahydrate calcium nitrate 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 dryer filled with 15 grams of ammonium bicarbonate, the mixture is kept stand at 40 ℃ for reaction for 48 hours, and the amorphous calcium carbonate nanospheres are obtained after centrifugation at 8000 revolutions per minute for 10 minutes.
(2) Dispersing the amorphous calcium carbonate nanospheres in 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 for 10 minutes at 8000 rpm to obtain the europium ion doped amorphous calcium carbonate nanospheres.
(3) Mixing 10 ml of ethanol suspension of europium ion doped amorphous calcium carbonate nanospheres with mass concentration of 2% and 60 ml of hydrogen peroxide aqueous solution with mass concentration of 20%, reacting for 1 hour, centrifuging at 8000 rpm for 10 minutes to obtain europium oxide doped hollow calcium carbonate nanospheres.
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 dryer filled with 15 g of ammonium bicarbonate, the mixture is kept stand at 40 ℃ for 48 hours, and the amorphous calcium carbonate nanospheres are obtained after centrifugation at 8000 rpm for 10 minutes.
(2) Dispersing amorphous calcium carbonate nanospheres in an ethanol solution of titanium chloride with the mass concentration of 3% to obtain amorphous calcium carbonate nanosphere suspension with the mass concentration of 20%, stirring for 30 minutes, and centrifuging for 10 minutes at 8000 rpm to obtain titanium ion doped amorphous calcium carbonate nanospheres.
(3) 10 ml of ethanol suspension of titanium ion doped amorphous calcium carbonate nanospheres with mass concentration of 2% and 60 ml of hydrogen peroxide aqueous solution with mass concentration of 20% are mixed and reacted for 1 hour, and the titanium dioxide doped hollow calcium carbonate nanospheres are obtained after centrifugation at 8000 revolutions per minute for 10 minutes.
Example 8
(1) 100 milliliters of a propanol solution of calcium chloride with the concentration of 0.05 mol/L is placed in a container with a plurality of air holes, then the container is placed in a drier filled with 1 gram of ammonium bicarbonate and ammonium carbonate (the total mass of the ammonium bicarbonate and the ammonium carbonate is 1 gram), and the mixture is kept standing at 20 ℃ for reaction for 6 hours, and is centrifuged at 2000 rpm for 30 minutes to obtain amorphous calcium carbonate nanospheres.
(2) Dispersing amorphous calcium carbonate nanospheres in a propanol solution of aluminum chloride with the mass concentration of 0.1% to obtain amorphous calcium carbonate nanosphere suspension with the mass concentration of 50%, stirring for 5 minutes, and centrifuging for 30 minutes at 2000 rpm to obtain aluminum ion doped amorphous calcium carbonate nanospheres.
(3) 10 ml of ethanol suspension of aluminum ion doped amorphous calcium carbonate nanospheres with mass concentration of 0.1% and 90 ml of hydrogen peroxide aqueous solution with mass concentration of 5% are mixed and reacted for 5 minutes, and the mixture is centrifuged at 2000 rpm for 30 minutes to obtain aluminum oxide doped hollow calcium carbonate nanospheres.
Example 9
(1) 50 milliliters of ethanol solution of calcium chloride with the concentration of 0.5 mol/liter is placed in a container with a plurality of air holes, then the container is placed in a dryer filled with 5 grams of ammonium bicarbonate, the mixture is kept stand at 30 ℃ for reaction for 20 hours, and the mixture is centrifuged at 4000 rpm for 25 minutes to obtain amorphous calcium carbonate nanospheres.
(2) Dispersing amorphous calcium carbonate nanospheres in an ethanol solution of nickel nitrate with the mass concentration of 10% to obtain 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 the nickel ion doped amorphous calcium carbonate nanospheres.
(3) 10 ml of ethanol suspension of nickel ion doped amorphous calcium carbonate nanospheres with the mass concentration of 50% and 10 ml of hydrogen peroxide water solution with the mass concentration of 80% are mixed and reacted for 40 minutes, and the nickel oxide doped hollow calcium carbonate nanospheres are obtained after 4000 revolutions per minute and centrifugation for 25 minutes.
Example 10
(1) 80 milliliters of ethanol solution of calcium chloride with the concentration of 0.2 millimoles per liter is placed in a container with a plurality of air holes, then the container is placed in a drier filled with 12 grams of ammonium bicarbonate, the mixture is kept stand at 40 ℃ for reaction for 36 hours, and the amorphous calcium carbonate nanospheres are obtained after centrifugation at 8000 revolutions per minute for 20 minutes.
(2) Dispersing amorphous calcium carbonate nanospheres in ethanol solution of lanthanum nitrate with the mass concentration of 10% to obtain 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) 10 ml of ethanol suspension of lanthanum ion doped amorphous calcium carbonate nanospheres with mass concentration of 7% and 5 ml of hydrogen peroxide aqueous solution with mass concentration of 60% are mixed and reacted for 2 hours, and centrifugation is carried out for 20 minutes at 8000 revolutions per minute to obtain lanthanum oxide doped hollow calcium carbonate nanospheres.
Example 11
(1) 150 ml of an 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 dryer filled with 25 g of ammonium bicarbonate, the mixture is kept standing at 50 ℃ for reaction for 120 hours, and the mixture is centrifuged at 13000 rpm for 10 minutes to obtain amorphous calcium carbonate nanospheres.
(2) Dispersing amorphous calcium carbonate nanospheres in an ethanol solution of cerium chloride with the mass concentration of 5% to obtain amorphous calcium carbonate nanosphere suspension with the mass concentration of 30%, stirring for 24 hours, and centrifuging for 10 minutes at 13000 rpm to obtain the amorphous calcium carbonate nanospheres doped with actinium oxide ions.
(3) Mixing 9 ml of ethanol suspension of cerium ion doped amorphous calcium carbonate nanospheres with mass concentration of 15% and 1 ml of hydrogen peroxide aqueous solution with mass concentration of 50%, reacting for 3 hours, and centrifuging for 10 minutes at 13000 rpm to obtain cerium oxide doped hollow calcium carbonate nanospheres.
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 stand at 25 ℃ for reaction for 80 hours, and the amorphous calcium carbonate nanospheres are obtained after centrifugation at 15000 rpm for 10 minutes.
(2) Dispersing amorphous calcium carbonate nanospheres in an ethanol solution of titanium chloride with the mass concentration of 8% to obtain amorphous calcium carbonate nanosphere suspension with the mass concentration of 40%, stirring for 16 hours, and centrifuging for 10 minutes at 15000 rpm to obtain titanium ion doped amorphous calcium carbonate nanospheres.
(3) 9 ml of ethanol suspension of titanium ion doped amorphous calcium carbonate nanospheres with mass concentration of 30% and 4 ml of hydrogen peroxide aqueous solution with mass concentration of 40% are mixed and reacted for 4 hours, and the mixture is centrifuged at 15000 r/min for 10 minutes to obtain the titanium dioxide doped hollow calcium carbonate nanospheres.
Example 13
(1) 100 milliliters of ethanol solution of calcium chloride with the concentration of 2 mol/L is placed in a container with a plurality of air holes, then the container is placed in a drier filled with 10 grams of ammonium bicarbonate, the mixture is kept stand at 35 ℃ for reaction for 60 hours, and the amorphous calcium carbonate nanospheres are obtained by centrifugation at 20000 revolutions per minute for 5 minutes.
(2) Dispersing amorphous calcium carbonate nanospheres in an ethanol solution of titanium chloride with the mass concentration of 6% to obtain amorphous calcium carbonate nanosphere suspension with the mass concentration of 25%, stirring for 10 hours, and centrifuging for 5 minutes at 20000 rpm to obtain titanium ion doped amorphous calcium carbonate nanospheres.
(3) Mixing 9 ml of ethanol suspension of titanium ion doped amorphous calcium carbonate nanospheres 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 for 5 minutes at 20000 revolutions per minute to obtain the titanium dioxide doped hollow calcium carbonate nanospheres.
Example 14
(1) 250 milliliters of ethanol solution of calcium chloride with the concentration of 0.2 mol/liter is placed in a container with a plurality of air holes, then the container is placed in a dryer filled with 15 grams of ammonium bicarbonate, the mixture is kept stand at 40 ℃ for reaction for 48 hours, and the mixture is centrifuged at 8000 revolutions per minute for 10 minutes to obtain amorphous calcium carbonate nanospheres.
(2) Dispersing amorphous calcium carbonate nanospheres in an ethanol solution of titanium chloride with the mass concentration of 3% to obtain amorphous calcium carbonate nanosphere suspension with the mass concentration of 20%, stirring for 30 minutes, and centrifuging for 10 minutes at 8000 rpm to obtain titanium ion doped amorphous calcium carbonate nanospheres.
(3) 10 ml of ethanol suspension of titanium ion doped amorphous calcium carbonate nanospheres with mass concentration of 2% and 60 ml of hydrogen peroxide aqueous solution with mass concentration of 20% are mixed and reacted for 1 hour, and the titanium dioxide doped hollow calcium carbonate nanospheres are obtained after centrifugation at 8000 revolutions per minute for 10 minutes.
The metal ion solution in the invention adopts the methanol, ethanol or propanol 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 lanthanoid to prepare the hollow calcium carbonate nanospheres doped with metal oxide or peroxide.
The foregoing is merely illustrative of the preferred embodiments of this invention, and it should be noted that modifications and extensions, such as sources of metal ions, could be made by those skilled in the art without departing from the principles of this invention, and such modifications and extensions should also be considered as being within the scope of this invention.
Claims (6)
1. The preparation method of the hollow calcium carbonate nanospheres doped with the metal oxide or the peroxide is characterized by comprising the following steps of:
(1) Dispersing amorphous calcium carbonate nanospheres in a metal ion alcohol solution, stirring, and centrifuging to obtain metal ion doped amorphous calcium carbonate nanospheres;
(2) Mixing an alcohol suspension of the amorphous calcium carbonate nanospheres doped with metal ions with an aqueous solution of hydrogen peroxide, and centrifuging after reaction to obtain metal oxide or peroxide doped hollow calcium carbonate nanospheres;
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 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 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 concentration of calcium ions in the alcohol solution is 0.2 millimoles/liter to 2 moles/liter; the diameter of the amorphous calcium carbonate nanospheres is 10-1000 nanometers;
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.
2. The method for preparing metal oxide or peroxide doped hollow calcium carbonate nanospheres according to claim 1, wherein the amorphous calcium carbonate nanospheres in step (1) are prepared by the following process: placing the alcoholic 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 at 20-50 ℃ for reaction for 6-5 days, 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 1, wherein the metal ion alcoholic solution in step (1) is a methanol, ethanol or propanol 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, lanthanoid.
4. The method for preparing metal oxide or peroxide doped hollow calcium carbonate nanospheres according to claim 1, wherein the alcohol in the step (1) and the step (2) is methanol, ethanol or propanol, the centrifugation speed is 2000-20000 rpm, and the centrifugation time is 5-30 minutes.
5. A metal oxide or peroxide doped hollow calcium carbonate nanosphere prepared according to the method of any one of claims 1 to 4, wherein the hollow calcium carbonate nanosphere has a hollow spherical structure with an average particle diameter of 10 nm to 1000 nm and a cavity diameter of 5 nm to 800 nm.
6. Use of the metal oxide or peroxide doped hollow calcium carbonate nanospheres of claim 5 in rubber, plastic, paper, ink, paint, commodity or pharmaceutical fields.
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