CN111170321B - Preparation method of nano hollow sphere containing graphitized carbon dots - Google Patents
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Abstract
The invention provides a preparation method of a hollow nanosphere containing graphitized carbon dots, which comprises the steps of firstly preparing silicon spheres containing aminopropyltriethoxysilane by using tetraethyl orthosilicate, hexadecyltrimethylammonium bromide, 1,2-bis (triethoxysilyl) ethane, aminopropyltriethoxysilane, ammonia water and hydrochloric acid as raw materials, then dispersing the silicon spheres in absolute ethyl alcohol, heating at a high temperature to form hollow silicon dioxide, and carbonizing the aminopropyltriethoxysilane and the absolute ethyl alcohol in the silicon spheres in the heating process, namely, the formation process of the hollow silicon dioxide nanoparticles and the graphitized carbon dots and the compounding process of the two nanoparticles are completed in one step in the high-temperature heating process. The preparation method provided by the invention has the advantages of simple process and low cost, and the obtained hollow silicon dioxide nano composite particles containing graphitized carbon dots have good biocompatibility and good application prospects in the fields of photo-thermal treatment, drug loading, drug slow release and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to a preparation method of a nano hollow sphere containing graphitized carbon dots.
Background
Graphitized carbon dots, that is, nano carbon particles having a graphite structure, include graphene quantum dots, carbon nano dots, and the like. The graphitized carbon dots have application prospects in drug delivery, photothermal therapy, photodynamic therapy, fluorescence imaging, biosensors, light-emitting diodes and the like. However, the function of the simple graphitized carbon dots is limited. The graphitized carbon dots are compounded with other materials to form composite particles with strong functions, so that the graphitized carbon dots can be promoted to be applied in wider fields. The composite particles are prepared by preparing several kinds of particles, and then assembling the particles into one particle by physical adsorption or chemical connection. For example, graphene quantum dots and gold nanoparticles are compounded, carbon black is treated by concentrated nitric acid to obtain graphene quantum dots with surface carboxylation, gold nanoparticles modified by mercaptoethylamine are synthesized, and then the graphene quantum dots and the gold nanoparticles are compounded together by a method of forming amide bonds between the surface carboxyl groups of the graphene quantum dots and the surface amino groups of the gold nanoparticles, so that the formed composite particles can be used for electrochemical detection of heavy metal ions [ silicon luminescence Ting, shu tying Ee, aryl anti-natharayanan, kam Chew Leong, peng Chen. For another example, graphene quantum dots and Mesoporous silica are compounded by synthesizing graphene quantum dots with carboxyl on the surface by using carbon black as a raw material, and simultaneously synthesizing Mesoporous silica with amino on the surface, then reacting the carboxyl on the graphene quantum dots with the amino on the surface of the Mesoporous silica, and connecting the graphene quantum dots and the Mesoporous silica together by amide bonds, so that the formed composite particles can be used for drug loading and photothermal therapy [ Yan Gao, shuangling Zhong, life Xu, shiha He, yueming Dou, shengnan Zha, pen Cheng, xuejun Cui.
The graphitized carbon dots and other materials are prepared in advance respectively and then are compounded, and the method has the defects that: the experimental process is complex, the complex process inevitably brings high cost, in addition, the graphitized carbon dots can only be compounded on the surface of another material, and the quantity of the graphitized carbon dots on the compounding is limited.
Disclosure of Invention
In order to overcome the defects of the existing method, the invention provides a one-pot method for compounding graphitized carbon dots and hollow silica nanoparticles, the graphitized carbon dots and the hollow silica are not required to be synthesized in advance and then compounded, but the graphitized carbon dots are formed simultaneously in the forming process of the hollow silica nanoparticles and are carried out in the same reaction system, and the compounding process of the graphitized carbon dots and the hollow silica nanoparticles is completed after the synthesis reaction is finished.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nano hollow sphere containing graphitized carbon dots comprises the following steps:
s1, synthesizing organic and inorganic hybrid silicon spheres: adding absolute ethyl alcohol, ammonia water and CTAB into deionized water, stirring, adding TEOS, BTSE and APTES into the mixed solution under the condition of stirring after the CTAB in the mixed solution is fully dissolved, uniformly stirring, centrifuging the reaction solution after stirring is finished, washing precipitates with the absolute ethyl alcohol and the deionized water respectively, and collecting the washed organic-inorganic hybrid silicon ball precipitates;
s2, performing warm treatment on the organic-inorganic hybrid silicon spheres, removing CTAB (cetyl trimethyl ammonium bromide), dispersing the organic-inorganic hybrid silicon spheres in absolute ethyl alcohol, adding the mixture into a reaction kettle, covering the reaction kettle tightly, heating at high temperature for reaction, naturally cooling to room temperature after the reaction is finished, and collecting a product; or
The organic-inorganic hybrid silicon spheres are dispersed in absolute ethyl alcohol after being subjected to warm-heat treatment, added into a reaction kettle, covered tightly, heated at high temperature for reaction, naturally cooled to room temperature after the reaction is finished, and a product is collected; or
Directly dispersing the organic-inorganic hybrid silicon spheres in absolute ethyl alcohol, adding the absolute ethyl alcohol into a reaction kettle, tightly covering the reaction kettle, heating the reaction kettle at a high temperature for reaction, naturally cooling the reaction kettle to room temperature after the reaction is finished, and collecting a product.
Further, in the step S1,
the volume ratio of the added absolute ethyl alcohol to the deionized water is 1:1 to 1:4, the volume ratio of the added ammonia water to the deionized water is 1;
the volume ratio of TEOS added to deionized water is 1 to 1, the volume ratio of BTSE added to deionized water is 1.
Further, the step S2 specifically includes:
s21, dispersing the organic-inorganic hybrid silicon spheres in deionized water, heating in a warm water bath, performing centrifugal treatment, and collecting precipitates;
s22, dispersing the precipitate into a mixed solution of absolute ethyl alcohol and hydrochloric acid, heating and stirring in a warm water bath, then carrying out centrifugal treatment and collecting the precipitate;
s23, repeating the steps S21-S22 for a plurality of times until CTAB in the precipitate is removed, and then collecting the precipitate and washing the precipitate once by using absolute ethyl alcohol and deionized water;
and S24, dispersing the precipitate in absolute ethyl alcohol, and adding the absolute ethyl alcohol into a reaction kettle for heating treatment.
Further, in the step S21, heating in a water bath at the temperature of 50-90 ℃ for 5-24h, then carrying out centrifugal treatment, and collecting precipitates;
in step S22, the volume ratio of the absolute ethyl alcohol to the hydrochloric acid is 500, the hydrochloric acid concentration is 37%, the mixture is heated and stirred in a water bath at the temperature of 50-90 ℃ for 2-12h, then centrifugal treatment is carried out, and precipitates are collected.
Further, the step S2 specifically includes:
s21, dispersing the organic-inorganic hybrid silicon ball precipitate in deionized water, heating in a water bath at the temperature of 50-90 ℃ for 5-24h, centrifuging, and washing the precipitate with absolute ethyl alcohol and deionized water;
s22, dispersing the precipitate in absolute ethyl alcohol, and adding the absolute ethyl alcohol into a reaction kettle for heating treatment.
Further, the step S2 specifically includes:
and directly dispersing the organic-inorganic hybrid silicon ball precipitate into absolute ethyl alcohol, and adding the absolute ethyl alcohol into a reaction kettle for heating treatment.
Further, the method is characterized in that the heating temperature of the reaction kettle is 300-550 ℃, and the heating time is 3-24h.
Further, after the step S2 is completed, the method further includes the following steps:
and S3, storing the obtained product in a dry powder state, or storing the product by dispersing the product in deionized water, or storing the product by dispersing the product in absolute ethyl alcohol.
The method for preparing the hollow silicon dioxide containing the graphitized carbon dots has the advantages of simple process and low cost. Because the hollow silica has a large inner cavity, the inner cavity and the shell layer both have a drug-loading function, the drug-loaded hollow silica has a slow-release function on the drug, and the graphitized carbon dots can be used for photo-thermal treatment and the like, thus the hollow silica containing the graphitized carbon dots is a multifunctional nano composite particle. The main chemical element of the graphitized carbon dots is carbon, the hollow silicon dioxide is biodegradable, and the degradation product has low toxicity or almost no toxicity, so that the hollow silicon dioxide nano composite particles containing the graphitized carbon dots, which are obtained by the invention, have good biocompatibility and good application prospects in the fields of photothermal therapy, drug loading, drug slow release and the like.
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In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
FIG. 1 is a schematic flow chart of a preparation method of a hollow nanosphere comprising graphitized carbon dots according to the present invention;
FIGS. 2a-2b are the product of isothermal heating at 500 ℃ for 3h according to example 1, FIG. 2a at low magnification and FIG. 2b at high magnification;
FIGS. 3a-3b are the product of isothermal heating at 500 ℃ for 6h according to example 1, FIG. 3a at low magnification and FIG. 3b at high magnification;
FIGS. 4a-4b are the product of isothermal heating at 500 ℃ for 9h according to example 1, FIG. 4a at low magnification and FIG. 4b at high magnification;
FIGS. 5a-5b are the product of isothermal heating at 500 ℃ for 15h according to example 1, FIG. 5a at low magnification and FIG. 5b at high magnification;
FIG. 6 is the product of isothermal heating at 500 ℃ for 15h according to example 2;
FIG. 7 is the product of isothermal heating at 500 ℃ for 15h according to example 3;
fig. 8 is a sample obtained according to example 4: changing the proportion of the precursor material to prepare a sample;
fig. 9 is a sample obtained according to example 5: samples prepared with varying ratios of precursor materials.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the present invention.
In the following description, for purposes of explanation, specific details are set forth, such as particular steps and particular structures, in order to provide a thorough understanding of the present invention. The following detailed description of the preferred embodiments of the invention, however, the invention is capable of other embodiments in addition to those detailed.
The invention provides a preparation method of a nano hollow sphere containing graphitized carbon dots, which takes tetraethyl orthosilicate (TEOS), cetyltrimethylammonium bromide (CTAB), 1,2-di (triethoxysilyl) ethane (1,2-Bis (triethoxysilyl) ethane, BTSE), aminopropyltriethoxysilane (Aminopropyltriethoxysilane, APTES), ammonia water, absolute ethyl alcohol and hydrochloric acid as raw materials for preparation. As shown in fig. 1, the preparation method is as follows:
firstly, synthesizing organic-inorganic hybrid silicon spheres, comprising the following steps: adding absolute ethyl alcohol, ammonia water (mass concentration: 28%) and CTAB into deionized water, wherein the volume ratio of the absolute ethyl alcohol to the deionized water is between 1:1 and 1:4, the volume ratio of the added ammonia water to the deionized water is between 1. Stirring the mixed solution at 5-50 ℃, adding TEOS, BTSE and APTES into the mixed solution under stirring after CTAB is fully dissolved, wherein the volume ratio of TEOS to deionized water is 1-1. And after stirring, centrifuging the reaction solution, washing the precipitate with absolute ethyl alcohol and deionized water respectively, and collecting the washed precipitate.
Then, the organic-inorganic hybrid silicon ball precipitate after washing is treated by any one of the following 3 methods:
the method comprises the following steps: dispersing organic-inorganic hybrid silicon ball precipitate in deionized water, heating in a water bath at 50-90 ℃ for 5-24h, centrifuging, collecting precipitate, dispersing the precipitate in a mixed solution of absolute ethyl alcohol and hydrochloric acid, wherein the volume ratio of the absolute ethyl alcohol to the hydrochloric acid (37%) is 500, heating and stirring in a water bath at 50-90 ℃ for 2-12h, centrifuging, collecting precipitate, performing warming treatment on the precipitate by using the mixed solution of the absolute ethyl alcohol and the hydrochloric acid by using the same method, repeatedly performing treatment on the precipitate by using the mixed solution of the absolute ethyl alcohol and the hydrochloric acid until CTAB in the precipitate is removed, collecting precipitate, washing the precipitate once by using the absolute ethyl alcohol and the deionized water, and performing the following treatment on the washed precipitate: dispersing the precipitate in absolute ethyl alcohol, injecting into a reaction kettle, covering the reaction kettle tightly, and carrying out solvothermal reaction for 3-24h at the temperature of 300-550 ℃. And after the reaction is finished, naturally cooling to room temperature, and collecting a product.
The method 2 comprises the following steps: dispersing the organic-inorganic hybrid silicon ball precipitate in deionized water, heating in a water bath at 50-90 ℃ for 5-24h, centrifuging, and washing the precipitate with absolute ethyl alcohol and deionized water. Dispersing the precipitate in absolute ethyl alcohol, injecting into a reaction kettle, covering the reaction kettle tightly, and carrying out solvothermal reaction for 3-24h at the temperature of 300-550 ℃. And after the reaction is finished, naturally cooling to room temperature, and collecting a product.
The method 3 comprises the following steps: dispersing the organic-inorganic hybrid silicon ball precipitate in absolute ethyl alcohol, then adding the mixture into a reaction kettle, tightly covering the reaction kettle, and carrying out solvothermal reaction for 3-24h at the temperature of 300-550 ℃. And after the reaction is finished, naturally cooling to room temperature, and collecting a product.
Finally, the obtained product is stored in a dry powder state, or is dispersed in deionized water for storage, or is dispersed in absolute ethyl alcohol for storage.
The following further description of some embodiments of the invention is provided:
example 1
Deionized water (375 mL), absolute ethanol (150 mL), and aqueous ammonia (28 wt%) (5 mL) were mixed, CTAB (0.81 g) was added to the mixture, heated to 35 ℃ with stirring, then TEOS (1 mL), BTSE (1 mL), and APTES (1 mL) were added to the mixture, stirring was continued at 35 ℃ for 24h, centrifuged, the precipitate was taken, washed 3 times with absolute ethanol and deionized water, respectively, and the precipitate was collected.
Adding 245mL of deionized water into the precipitate, heating the precipitate in a 500mL glass bottle in a 70 ℃ constant-temperature water bath for 12h, naturally cooling the precipitate to room temperature, centrifuging the precipitate, adding absolute ethyl alcohol (250 mL) and hydrochloric acid (0.5 mL and 37%), heating the precipitate in a 60 ℃ constant-temperature water bath for 5h, naturally cooling the precipitate to room temperature, centrifuging the precipitate to obtain silicon spheres with CTAB removed, washing the silicon spheres with the absolute ethyl alcohol and the deionized water, and dispersing the silicon spheres in 45mL of absolute ethyl alcohol to form a silicon sphere suspension.
2mL of the anhydrous ethanol silicon sphere suspension is taken and transferred into a reaction kettle, the anhydrous ethanol is used for diluting the suspension to 25mL, and the reaction kettle is sealed. A total of 7 parts of such samples were prepared. That is, the 7 closed reaction vessels contained the same suspension. And placing 5 reaction kettles in a muffle furnace at 500 ℃ for constant temperature for 3h, 6h, 9h, 15h and 24h respectively. The other 2 reaction kettles are respectively placed in the reaction kettles with the temperature of 400 ℃ and 550 ℃ to be heated for 15 hours. The sample was naturally cooled to room temperature. The samples were stored in the dry powder state.
The results show that the obtained sample is gray in appearance, the microscopic morphology is a hollow structure, the particle size of the microspheres is mainly distributed between 300 nm and 400nm, as shown in the attached figures 2a to 5b, the hollow microspheres are further amplified and visible, and the microspheres contain a large amount of particles with the particle size of about 10 nm. The Raman spectrum detection result shows that the hollow microsphere has two characteristic peaks, namely a D peak and a G peak which are characteristic peaks of a graphite structure, so that the fine nano particles in the microsphere mainly consist of graphitized carbon dots.
Example 2
Deionized water (375 mL), absolute ethanol (150 mL), and aqueous ammonia (28 wt%) (5 mL) were mixed, CTAB (0.81 g) was added to the mixture, heated to 35 ℃ with stirring, then TEOS (1 mL), BTSE (1 mL), and APTES (1 mL) were added to the mixture, stirring was continued at 35 ℃ for 24h, centrifuged, the precipitate was taken, the precipitate was washed 3 times with absolute ethanol and deionized water, respectively, and the precipitate was collected.
Adding 245mL of deionized water into the precipitate, heating the precipitate in a 500mL glass bottle in a constant-temperature water bath at 70 ℃ for 12h, naturally cooling the precipitate to room temperature, centrifuging the precipitate, washing the precipitate with absolute ethyl alcohol and deionized water, and dispersing the precipitate in 45mL of absolute ethyl alcohol to obtain silicon spheres without CTAB.
And (3) taking 2mL of the absolute ethyl alcohol silicon sphere suspension, transferring the absolute ethyl alcohol silicon sphere suspension into a reaction kettle, diluting the absolute ethyl alcohol suspension to 25mL, sealing the reaction kettle, keeping the temperature of the reaction kettle constant in a muffle furnace at 500 ℃ for 15h respectively, and naturally cooling the sample to room temperature. The samples were stored in the dry powder state.
The experimental result is shown in figure 6, and the obtained microspheres are also hollow structures, the particle sizes are mainly distributed between 300 and 400nm, and a large number of graphitized carbon dots are contained.
Example 3
Deionized water (375 mL), absolute ethanol (150 mL), and ammonia (28 wt%) (5 mL) were mixed, CTAB (0.81 g) was added to the mixture, heated to 35 ℃ with stirring, then TEOS (1 mL), BTSE (1 mL), and APTES (1 mL) were added to the mixture, stirring was continued at 35 ℃ for 24h, centrifuged, the precipitate was taken, washed 3 times with absolute ethanol and deionized water, respectively, collected, and re-dispersed in 45mL of absolute ethanol.
And (3) taking 2mL of the absolute ethyl alcohol silicon sphere suspension, transferring the absolute ethyl alcohol silicon sphere suspension into a reaction kettle, diluting the absolute ethyl alcohol suspension to 25mL, sealing the reaction kettle, keeping the temperature of the reaction kettle constant in a muffle furnace at 500 ℃ for 15h respectively, and naturally cooling the sample to room temperature.
The experimental result is shown in figure 7, the microsphere is a hollow structure, the particle size is mainly distributed between 300-400nm, and a large number of graphitized carbon dots are contained. Except that the morphology of the microspheres was different from that of the hollow microspheres obtained by examples 1-2, that is, the density difference between the shell and the internal cavity was not as significant as that of the hollow microspheres obtained by examples 1-2, although the microspheres were also hollow structures.
Example 4
50mL of deionized water, 50mL of anhydrous ethanol and 830 μ L of ammonia water (28 wt%) are mixed, 1g of CTAB (i.e., the volume ratio of the anhydrous ethanol to the deionized water is 1:1, the volume ratio of the ammonia water to the deionized water is 1. Stirring was continued for 24h at 35 ℃. Centrifuging, washing the precipitate with absolute ethyl alcohol and deionized water, dispersing the precipitate in 245mL of deionized water, heating in 70 ℃ water bath for 12h, then centrifuging, adding absolute ethyl alcohol (250 mL) and hydrochloric acid (0.5 mL, 37%) into the precipitate, heating in 60 ℃ constant-temperature water bath for 5h, then naturally cooling to room temperature, centrifuging to obtain silicon spheres with CTAB removed, washing the silicon spheres with absolute ethyl alcohol and deionized water once respectively, and dispersing the silicon spheres in 45mL of absolute ethyl alcohol to form a silicon sphere suspension. And (3) taking 2mL of the absolute ethyl alcohol silicon sphere suspension, transferring the absolute ethyl alcohol silicon sphere suspension into a reaction kettle, diluting the absolute ethyl alcohol suspension to 25mL, sealing the reaction kettle, keeping the temperature of the reaction kettle in a muffle furnace at 500 ℃ for 15h, and naturally cooling the sample to room temperature. As a result, hollow microspheres containing graphitized carbon dots were obtained (FIG. 8).
Example 5
Mixing 80mL of deionized water, 20mL of anhydrous ethanol and 900 μ L of ammonia (28 wt%), adding 0.16g of CTAB (i.e., the volume ratio of anhydrous ethanol to deionized water is 1:4, the volume ratio of ammonia to deionized water is 1. Stirring was continued for 24h at 35 ℃. Centrifuging, washing the precipitate with absolute ethyl alcohol and deionized water, dispersing the precipitate in 245mL of deionized water, heating in a 70 ℃ water bath for 12h, then centrifuging, adding absolute ethyl alcohol (250 mL) and hydrochloric acid (0.5 mL, 37%) into the precipitate, heating in a 60 ℃ constant-temperature water bath for 5h, then naturally cooling to room temperature, centrifuging to obtain silicon spheres with CTAB removed, washing the silicon spheres with absolute ethyl alcohol and deionized water once respectively, and dispersing the silicon spheres in 20mL of absolute ethyl alcohol to form a silicon sphere suspension. And (3) taking 2mL of the absolute ethyl alcohol silicon sphere suspension, transferring the absolute ethyl alcohol silicon sphere suspension into a reaction kettle, diluting the absolute ethyl alcohol suspension to 25mL, sealing the reaction kettle, keeping the temperature of the reaction kettle in a muffle furnace at 500 ℃ for 15h, and naturally cooling the sample to room temperature. The result is a scientific microsphere with small particle size, mainly distributed between 100-200nm, and containing graphitized carbon dots, as shown in figure 9.
Example 6
Deionized water (375 mL), absolute ethanol (150 mL), and aqueous ammonia (28 wt%) (5 mL) were mixed, CTAB (0.81 g) was added to the mixture, heated to 35 ℃ with stirring, then TEOS (1 mL), BTSE (1 mL), and APTES (1 mL) were added to the mixture, stirring was continued at 35 ℃ for 24h, centrifuged, the precipitate was taken, the precipitate was washed 3 times with absolute ethanol and deionized water, respectively, and the precipitate was collected.
Adding 245mL of deionized water into the precipitate, heating the precipitate in a 500mL glass bottle in a 50 ℃ constant-temperature water bath for 24h, naturally cooling the precipitate to room temperature, centrifuging the precipitate, adding absolute ethyl alcohol (250 mL) and hydrochloric acid (0.5 mL and 37%), heating the precipitate in a 90 ℃ constant-temperature water bath for 2h, naturally cooling the precipitate to room temperature, centrifuging the precipitate to obtain silicon spheres with CTAB removed, washing the silicon spheres once by using the absolute ethyl alcohol and the deionized water respectively, and dispersing the silicon spheres in 45mL of absolute ethyl alcohol to form a silicon sphere suspension.
Taking 2mL of the anhydrous ethanol silicon sphere suspension, transferring the anhydrous ethanol silicon sphere suspension into a reaction kettle, diluting the anhydrous ethanol suspension to 25mL, sealing the reaction kettle, keeping the temperature in a muffle furnace at 500 ℃ for 15h, and naturally cooling to room temperature. As a result, hollow microspheres containing graphitized carbon dots were obtained. The microspheres are dispersed in deionized water, and the structure is stable.
Example 7
Deionized water (375 mL), absolute ethanol (150 mL), and aqueous ammonia (28 wt%) (5 mL) were mixed, CTAB (0.81 g) was added to the mixture, heated to 35 ℃ with stirring, then TEOS (1 mL), BTSE (1 mL), and APTES (1 mL) were added to the mixture, stirring was continued at 35 ℃ for 24h, centrifuged, the precipitate was taken, the precipitate was washed 3 times with absolute ethanol and deionized water, respectively, and the precipitate was collected.
Adding 245mL of deionized water into the precipitate, heating the precipitate in a 500mL glass bottle in a constant-temperature water bath at 90 ℃ for 5h, naturally cooling the precipitate to room temperature, centrifuging the precipitate, adding absolute ethyl alcohol (250 mL) and hydrochloric acid (0.5 mL and 37%), heating the precipitate in a constant-temperature water bath at 50 ℃ for 12h, naturally cooling the precipitate to room temperature, centrifuging the precipitate to obtain silicon spheres without CTAB, washing the silicon spheres once by using the absolute ethyl alcohol and the deionized water respectively, and dispersing the silicon spheres in 45mL of absolute ethyl alcohol to form a silicon sphere suspension.
Taking 2mL of the anhydrous ethanol silicon sphere suspension, transferring the anhydrous ethanol silicon sphere suspension into a reaction kettle, diluting the anhydrous ethanol suspension to 25mL, sealing the reaction kettle, keeping the temperature in a muffle furnace at 500 ℃ for 15h, and naturally cooling to room temperature. As a result, hollow microspheres containing graphitized carbon dots were obtained.
The above description is of the preferred embodiment of the invention. It is to be understood that the invention is not limited to the particular embodiments described above, in that devices and structures not described in detail are understood to be implemented in a manner common in the art; those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or modify equivalent embodiments to equivalent variations, without departing from the spirit of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are within the scope of the technical solution of the present invention, unless the technical essence of the present invention is not departed from the content of the technical solution of the present invention.
Claims (6)
1. A preparation method of a nano hollow sphere containing graphitized carbon dots is characterized by comprising the following steps:
s1, synthesizing organic-inorganic hybrid silicon spheres: adding absolute ethyl alcohol, ammonia water and CTAB into deionized water, stirring, adding TEOS, BTSE and APTES into the mixed solution under the condition of stirring after the CTAB in the mixed solution is fully dissolved, uniformly stirring, centrifuging the reaction solution after stirring, washing precipitates with the absolute ethyl alcohol and the deionized water respectively, collecting the washed organic-inorganic hybrid silica ball precipitates, wherein the volume ratio of the added absolute ethyl alcohol to the deionized water is between 1:1 and 1:4, the volume ratio of the added ammonia water to the deionized water is between 1 and 60; the volume ratio of TEOS added to deionized water is 1 to 1, the volume ratio of BTSE added to deionized water is 1;
s2, performing warm treatment on the organic-inorganic hybrid silicon spheres, removing CTAB (cetyl trimethyl ammonium bromide), dispersing the organic-inorganic hybrid silicon spheres in absolute ethyl alcohol, adding the mixture into a reaction kettle, covering the reaction kettle tightly, heating at high temperature for reaction, naturally cooling to room temperature after the reaction is finished, and collecting a product; or
The organic-inorganic hybrid silicon spheres are dispersed in absolute ethyl alcohol after being subjected to warm-heat treatment, added into a reaction kettle, covered tightly, heated at high temperature for reaction, naturally cooled to room temperature after the reaction is finished, and a product is collected; or
Directly dispersing the organic-inorganic hybrid silicon spheres in absolute ethyl alcohol, adding the anhydrous ethyl alcohol into a reaction kettle, tightly covering the reaction kettle, heating at high temperature for reaction, naturally cooling to room temperature after the reaction is finished, and collecting a product;
the heating temperature of the reaction kettle is 300-550 ℃, and the heating time is 3-24h.
2. The method for preparing a hollow nanosphere comprising graphitized carbon dots according to claim 1, wherein the step S2 specifically comprises:
s21, dispersing the organic-inorganic hybrid silicon spheres in deionized water, heating in a warm water bath, performing centrifugal treatment, and collecting precipitates;
s22, dispersing the precipitate into a mixed solution of absolute ethyl alcohol and hydrochloric acid, heating and stirring in a warm water bath, then carrying out centrifugal treatment and collecting the precipitate;
s23, repeating the steps S21-S22 for a plurality of times until CTAB in the precipitate is removed, and then collecting the precipitate and washing the precipitate once by using absolute ethyl alcohol and deionized water;
and S24, dispersing the precipitate in absolute ethyl alcohol, and adding the absolute ethyl alcohol into a reaction kettle for high-temperature heating treatment.
3. The method for preparing the hollow nanospheres containing the graphitized carbon dots as claimed in claim 2, wherein in the step S21, the hollow nanospheres are heated in a water bath at a temperature of 50 to 90 ℃ for 5 to 24 hours, then are subjected to centrifugal treatment, and are collected and precipitated;
in step S22, the volume ratio of absolute ethyl alcohol to hydrochloric acid is 500.
4. The method for preparing the hollow nanosphere comprising the graphitized carbon dot as claimed in claim 1, wherein the step S2 specifically comprises:
s21, dispersing the organic-inorganic hybrid silicon ball precipitate in deionized water, heating in a water bath at the temperature of 50-90 ℃ for 5-24h, centrifuging, and washing the precipitate with absolute ethyl alcohol and deionized water;
s22, dispersing the precipitate in absolute ethyl alcohol, and adding the absolute ethyl alcohol into a reaction kettle for high-temperature heating treatment.
5. The method for preparing a hollow nanosphere comprising graphitized carbon dots according to claim 1, wherein the step S2 specifically comprises:
and directly dispersing the organic-inorganic hybrid silicon ball precipitate into absolute ethyl alcohol, and adding the mixture into a reaction kettle for high-temperature heating treatment.
6. The method for preparing the hollow nanospheres containing graphitized carbon dots according to claim 1, wherein the step S2 is further completed and then comprises the following steps:
and S3, storing the obtained product in a dry powder state, or storing the product by dispersing the product in deionized water, or storing the product by dispersing the product in absolute ethyl alcohol.
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| CN102276764A (en) * | 2011-06-16 | 2011-12-14 | 新丰见微化工实业有限公司 | Chemical modification method of polymer powder |
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| CN102716745A (en) * | 2011-03-29 | 2012-10-10 | 中国科学院大连化学物理研究所 | Preparation method for yolk-eggshell-type organic-inorganic hybrid silicon oxide nanosphere |
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| CN105271266A (en) * | 2015-10-21 | 2016-01-27 | 哈尔滨工程大学 | Preparation method of multifunctional mesoporous Gd-Si-Ce6 nanocomposite with core-shell structure |
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