CN115193349B - Preparation method of porous hollow carbon nanospheres - Google Patents
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- CN115193349B CN115193349B CN202210683075.9A CN202210683075A CN115193349B CN 115193349 B CN115193349 B CN 115193349B CN 202210683075 A CN202210683075 A CN 202210683075A CN 115193349 B CN115193349 B CN 115193349B
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Abstract
The application provides a preparation method of a porous hollow carbon nanosphere, which relates to the technical field of material preparation and comprises the following steps: adding silicon dioxide into acetic acid solution of chitosan, stirring, dripping sodium tripolyphosphate aqueous solution, sealing, reacting, and magnetically stirring to obtain a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid aqueous phase system; mixing isooctyl palmitate, jojoba oil, sixteen-stearyl alcohol and an emulsifier, heating and stirring until the mixture is dissolved to obtain an oil phase, adding the oil phase into the polymer colloid water phase system, and stirring to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silicon dioxide core material coated with grease; then freeze-drying and high-temperature calcining to obtain porous carbon nanospheres with silicon dioxide as a core; and etching the porous carbon nanospheres with the silicon dioxide as the core to obtain the porous hollow carbon nanospheres. The carbon nanospheres of the application have good dispersibility, no pore-forming agent is required to be added, the preparation method is simple, and the cost is low.
Description
Technical Field
The application relates to the technical field of material preparation, in particular to a preparation method of a porous hollow carbon nanosphere.
Background
The porous hollow carbon microsphere is a hollow carbon material with regular spherical morphology and rich gaps on the spherical wall, and is divided into microporous carbon microsphere (aperture <2 nm), mesoporous carbon microsphere (aperture <50 nm) and macroporous carbon microsphere (aperture >50 nm) according to the aperture size, and the morphology brings rich structural performance to the carbon nanosphere. The hollow interior structure of the porous hollow carbon microsphere provides a higher loading space than the carbon nanospheres; the porous sphere wall increases the void ratio and specific surface area of the carbon nanospheres, and enhances the embedding, adsorption and fixing capabilities of the preloaded matters; meanwhile, the existence of the pore canal provides a convenient channel for the preloaded matters to permeate into the carbon sphere, so that the permeability is improved. In addition, the porous hollow carbon nanospheres have the advantages of high conductivity, low density, good chemical stability, good biocompatibility, good designability and the like, and particularly can be designed to obtain porous carbon microspheres with different pore structures and microsphere particle diameters by changing the preparation method. Therefore, the porous hollow carbon nanospheres have good application prospects in the fields of catalysis, adsorption, energy storage, biological medicine and the like.
The preparation method of the porous hollow carbon nanospheres at the present stage generally adopts a template method, and has the advantages of simple process, good repeatability and the like. However, when the porous hollow carbon nanospheres are prepared by the template method, a cross-linking agent and an inducer are required to be added, so that the preparation cost of the carbon nanospheres is increased, other elements are easy to introduce, the structure of the carbon nanospheres is influenced, and the industrialized popularization of the carbon nanospheres is not facilitated.
Disclosure of Invention
The application solves the problem that the preparation cost is increased due to the addition of a cross-linking agent and an inducer when preparing the porous hollow carbon nanospheres by a template method.
In order to solve the problems, the application provides a preparation method of a porous hollow carbon nanosphere, which comprises the following steps:
step S1: adding silicon dioxide into acetic acid solution of chitosan, stirring, dripping sodium tripolyphosphate aqueous solution, sealing, reacting, and magnetically stirring to obtain a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid aqueous phase system;
step S2: mixing isooctyl palmitate, jojoba oil, sixteen-stearyl alcohol and an emulsifier, heating and stirring until the mixture is dissolved to obtain an oil phase, adding the oil phase into the chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid water phase system, and stirring to obtain an oil-in-water emulsion of a chitosan/sodium tripolyphosphate/silicon dioxide core material coated with grease;
step S3: the oil-in-water emulsion of the chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by the grease is subjected to freeze drying and high-temperature calcination to obtain the porous carbon nanospheres with the silicon dioxide as the core;
step S4: and placing the porous carbon nanospheres with the silicon dioxide as a core in hydrofluoric acid solution, stirring, centrifuging and washing to be neutral to obtain the porous hollow carbon nanospheres.
Further, in step S1, the magnetic stirring includes: magnetically stirring the water area at 45-55 ℃; the time of the sealing reaction is 10 hours.
Further, in step S2, after mixing isooctyl palmitate, jojoba oil, sixteen-stearyl alcohol and an emulsifier, heating and stirring until the mixture is dissolved to obtain an oil phase, which includes:
mixing the isooctyl palmitate, the jojoba oil and the hexadecyl-octadecanol, heating to 80 ℃, stirring until the mixture is uniformly dissolved, adding an emulsifying agent, and continuously stirring until the mixture is uniformly dissolved at the temperature of 80 ℃ to obtain an oil phase.
Further, in step S2, the emulsifier is cetyl glucoside.
Further, in step S2, the oil phase is added to the chitosan/sodium tripolyphosphate/silica polymer colloid water phase system and stirred, so as to obtain an oil-in-water emulsion with the chitosan/sodium tripolyphosphate/silica core material coated with grease, which comprises:
under the condition that the water area temperature is 80 ℃, the oil phase is rapidly added into the chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid water phase system while stirring, the mixture is stirred and homogenized, and the temperature is reduced to the room temperature, so that the oil-in-water emulsion of the chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by the grease is obtained.
Further, in step S2, the stirring time is 10min, and the homogenizing time is 3-5min.
Further, in step S3, the high-temperature calcination includes: heating to 400-500 ℃ at a speed of 2-5 ℃/min under the protection of nitrogen, and preserving heat for 1-2h; then heating to 950-1050 ℃ at a rate of 5-10 ℃ and preserving heat for 3-4h.
Further, in step S3, before calcining at high temperature, the oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material coated with the oil after freeze drying is added into low temperature absolute ethanol to be dispersed uniformly, and is filtered and dried in vacuum.
Further, in step S3, the temperature of the absolute ethanol is-10 ℃.
Further, in the step S4, the stirring time is 10-12h.
Compared with the prior art, the preparation method of the porous hollow carbon nanospheres has the advantages that:
(1) According to the application, silicon dioxide is added into acetic acid solution of chitosan and stirred, then sodium tripolyphosphate aqueous solution is slowly added dropwise, sealing reaction and magnetic stirring are carried out, so that a polymer colloid aqueous phase system is formed by the acetic acid solution of chitosan and the sodium tripolyphosphate aqueous solution through a polyelectrolyte compounding mechanism, the silicon dioxide can be uniformly suspended in a gel system, a micro-capsule sphere structure with the silicon dioxide as a core and chitosan/sodium tripolyphosphate gel as a wall material can be effectively formed, and a sphere center template is provided for carbon nanosphere formation;
(2) In an emulsion system formed by a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid system which takes isooctyl palmitate, jojoba oil, sixteen-stearyl alcohol and an emulsifier as oil phases and water phases under the action of high-speed shearing force, the oil phases are crosslinked with the chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid water phase system through H-O coordination, a composite nano microsphere disperse phase which is formed by taking silicon dioxide as a core, a chitosan/sodium tripolyphosphate layer and an oil layer as an outermost layer and sequentially taking silicon dioxide as a core is formed under the action of the emulsifier, the lipophilic group of the emulsifier is combined with the oil phase of the inner layer of the microsphere, hydrophilic groups are combined with continuous phase water, and nano microspheres are uniformly dispersed in the water phase without being connected, so that the uniformly dispersed and independent carbon nano spheres are formed;
(3) The chitosan and the oil phase contain a large number of oxygen-containing functional groups, most of the oxygen-containing functional groups are broken and escaped in the high-temperature calcination process, so that the graphitized wall layer of the carbon nanosphere has a cavity, and the pore-forming of the carbon nanosphere is completed.
Drawings
Fig. 1 is a flowchart of a preparation method of a porous hollow carbon nanosphere according to an embodiment of the present application.
Detailed Description
In order that the above objects, features and advantages of the application will be readily understood, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It should be noted that in the description of embodiments of the present application, the description of the term "some specific embodiments" means that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same implementations or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
As shown in fig. 1, the present application provides a method for preparing a porous hollow carbon nanosphere, comprising the steps of:
step S1: adding silicon dioxide into acetic acid solution of chitosan, stirring, dripping sodium tripolyphosphate aqueous solution, sealing, reacting, and magnetically stirring to obtain a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid aqueous phase system;
step S2: mixing isooctyl palmitate, jojoba oil, sixteen-stearyl alcohol and an emulsifier, heating and stirring until the mixture is dissolved to obtain an oil phase, adding the oil phase into a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid water phase system, and stirring to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silicon dioxide core materials coated with grease;
step S3: the oil-in-water emulsion of chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by grease is subjected to freeze drying and high-temperature calcination to obtain porous carbon nanospheres with silicon dioxide as a core;
step S4: and placing the porous carbon nanospheres with the silicon dioxide as a core in hydrofluoric acid solution, stirring, centrifuging and washing to be neutral to obtain the porous hollow carbon nanospheres.
According to the embodiment of the application, the silicon dioxide is added into the acetic acid solution of chitosan and stirred, then the sodium tripolyphosphate aqueous solution is slowly dripped, the sealing reaction and the magnetic stirring are carried out, so that the acetic acid solution of chitosan and the sodium tripolyphosphate aqueous solution form a polymer colloid aqueous phase system through a polyelectrolyte compounding mechanism, the silicon dioxide can be uniformly suspended in a gel system, a micro-capsule sphere structure with the silicon dioxide as a core and the chitosan/sodium tripolyphosphate gel as a wall material can be effectively formed, and a sphere center template is provided for the formation of the carbon nanospheres.
In the embodiment of the application, isooctyl palmitate, jojoba oil, sixteen-stearyl alcohol and an emulsifier are used as oil phases and aqueous phases in an emulsion system formed by a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid system under the action of high-speed shearing force, the oil phases are crosslinked with the chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid aqueous phase system through H-O coordination, a composite nano microsphere disperse phase which is formed by taking silicon dioxide as a core, a chitosan/sodium tripolyphosphate layer and an oil layer as an inner layer sequentially is formed under the action of the emulsifier, the lipophilic groups of the emulsifier are combined with the oil phases of the inner layers of the microsphere, hydrophilic groups are combined with continuous phase water, so that the nano microsphere is uniformly dispersed in the aqueous phase without connection, the uniformly dispersed and independent carbon nano sphere is formed, and the dispersibility of the carbon nano sphere is improved.
According to the embodiment of the application, the chitosan and the oil phase contain a large number of oxygen-containing functional groups, most of the oxygen-containing functional groups are broken and escaped due to C-O bond breakage in the high-temperature calcination process, so that the graphitized wall layer of the carbon nanosphere has a cavity, and the carbon nanosphere pore-forming is completed.
Specifically, the embodiment of the application adopts a hard template method, wherein the common hard template method is to immerse hard template agent silicon dioxide into carbon precursor in a liquid phase state to carry out polymerization and crosslinking, carbonize in inert atmosphere and etch the hard template agent by solution so as to obtain the hollow carbon nanospheres. Usually, a cross-linking agent and an inducer are required to be added, so that the preparation cost of the carbon nanospheres is increased, and other elements are easy to introduce. In the preparation process of the porous hollow carbon nanospheres, the preparation process is optimized, additives such as a cross-linking agent, an inducer, a pore-forming agent and the like are not needed to be added, and the manufacturing cost is reduced.
In some specific embodiments, in step S1, the magnetic stirring comprises: magnetically stirring the water area at 45-55 ℃; the time for the sealing reaction was 10 hours. Under the sealing condition, the micro-capsule ball structure taking silicon dioxide as a core and chitosan/sodium tripolyphosphate gel as a wall material is formed by magnetic stirring acceleration, so that a sphere center template is provided for the formation of the carbon nanospheres.
In some specific embodiments, in step S2, after mixing isooctyl palmitate, jojoba oil, sixteen-stearyl alcohol, and an emulsifier, heating and stirring until dissolved to obtain an oil phase, comprising:
mixing isooctyl palmitate, jojoba oil and hexadecyl-octadecanol, heating to 80deg.C, stirring, adding emulsifier, and stirring at 80deg.C to obtain oil phase.
In the heating and stirring process of the embodiment, the stirring temperature is kept at 80 ℃, which is favorable for uniform dissolution among the two.
In some specific embodiments, in step S2, the emulsifier is cetyl glucoside. Therefore, the raw materials are easy to obtain, and the emulsifying effect is good.
In some specific embodiments, in step S2, the oil phase is added to the chitosan/sodium tripolyphosphate/silica polymer colloidal aqueous phase system and stirred to obtain an oil-in-water emulsion of the oil-in-water type chitosan/sodium tripolyphosphate/silica core material coated with the oil, comprising:
under the condition that the water area temperature is 80 ℃, the oil phase is rapidly added into a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid water phase system while stirring, the mixture is stirred and homogenized, and the temperature is reduced to the room temperature, so that the oil-in-water emulsion of the chitosan/sodium tripolyphosphate/silicon dioxide core material coated by grease is obtained.
In this embodiment, in order to ensure the emulsification effect and prevent segregation or delamination, the oil phase needs to be stirred, so when the oil phase is added into the chitosan/sodium tripolyphosphate/silica polymer colloid aqueous phase system, the stirring state is kept at the temperature of 80 ℃ all the time, and meanwhile, the oil phase is sufficiently dispersed into small droplets by homogenizing, so that the emulsifier is facilitated to sufficiently pack the oil phase or the aqueous phase to form finer emulsified particles, the stability of the product is facilitated, and finally, the oil-in-water emulsion of the chitosan/sodium tripolyphosphate/silica core material wrapped by the oil is obtained by emulsification.
In some specific embodiments, in step S2, the stirring time is 10min and the homogenizing time is 3-5min. Therefore, the full emulsification is realized, and the grease is wrapped on the chitosan/sodium tripolyphosphate/silicon dioxide core material.
In some specific embodiments, in step S3, the high temperature calcination comprises: heating to 400-500 ℃ at a speed of 2-5 ℃/min under the protection of nitrogen, and preserving heat for 1-2h; then heating to 950-1050 ℃ at a rate of 5-10 ℃ and preserving heat for 3-4h.
Therefore, the chitosan and a large amount of oxygen-containing functional groups in the oil phase are subjected to high-temperature calcination to break and escape through C-O bond breaking, so that the graphitized wall layer of the carbon nanosphere has a cavity, and the carbon nanosphere pore-forming is completed. The pore-forming method is simple, no pore-forming agent is required to be added, the preparation method is simple, the condition is mild, and the control is easy.
In some specific embodiments, in step S3, the method further comprises adding the oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material coated with the lyophilized oil into low-temperature absolute ethanol, dispersing uniformly, filtering, and vacuum drying.
In the embodiment, the ethanol is a polar molecule, the solubility of the ethanol to the grease is extremely low at low temperature, the low-temperature ethanol is used as a dispersing agent to disperse the emulsion, and the continuous phase volume is increased by being compatible with the water phase under the condition of not damaging the emulsion microsphere, so that the independent dispersion and the subsequent carbonization pore-forming of the emulsion microsphere are more facilitated.
In some specific embodiments, in step S3, the temperature of the absolute ethanol is-10 ℃.
In the embodiment, the ethanol is cooled to below-10 ℃ to disperse the prepared emulsion, so that the emulsion microsphere is not damaged, and the emulsion microsphere is compatible with water phase, thus being more beneficial to independent dispersion and subsequent carbonization pore-forming of the emulsion microsphere.
In some specific embodiments, in step S4, the stirring time is 10-12 hours. Thereby achieving sufficient etching of the silicon dioxide template.
Example 1
The porous hollow carbon nanospheres are prepared by the preparation method of the porous hollow carbon nanospheres, and the preparation method comprises the following steps:
step S1: adding 0.25g of chitosan into 50mL of 1% acetic acid solution, putting into a round-bottom flask, magnetically stirring and dissolving, adding 0.1g of silicon dioxide into the acetic acid solution of chitosan, magnetically stirring and dispersing uniformly; and (3) weighing 0.05g of sodium tripolyphosphate, dissolving with 10mL of distilled water, placing in a constant pressure funnel, slowly dripping into the chitosan/silicon dioxide solution for 30min, and performing closed reaction for 10h under magnetic stirring in a water area at 50 ℃ to obtain a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid water phase system.
Step S2: mixing 3.4g of isooctyl palmitate, 3.4g of jojoba oil and 3.4g of hexadecyl-octadecanol, stirring and heating to 80 ℃, adding an emulsifier cetyl glucoside after uniform dissolution, and stirring and dissolving uniformly at 80 ℃ to obtain an oil phase; transferring the water phase system in the step S1 into a beaker, placing the beaker into a water area, heating to 80 ℃, adding the oil phase into the water phase system rapidly under stirring, stirring for 10min, homogenizing for 3min, and cooling to room temperature to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by grease;
step S3: placing the oil-in-water emulsion of the chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by the grease into a freeze dryer for freeze drying to obtain freeze-dried powder; adding the freeze-dried powder into absolute ethyl alcohol at the temperature of minus 10 ℃ to be uniformly dispersed, carrying out suction filtration and vacuum drying to obtain dry powder; placing the dry powder in a quartz boat, heating to 450 ℃ at a speed of 2 ℃/min under the protection of nitrogen, and preserving heat for 1h at the temperature; then heating to 1000 ℃ at a rate of 5 ℃, and preserving heat for 3.5 hours at the temperature; cooling to room temperature under the protection of nitrogen to obtain porous carbon nanospheres with silicon dioxide as a core;
step S4: and (3) placing the porous carbon nanospheres with the silicon dioxide as the core in hydrofluoric acid solution, stirring at room temperature for reacting for 11 hours, centrifugally separating, and washing to be neutral to obtain the porous hollow carbon nanospheres.
Example 2
The porous hollow carbon nanospheres are prepared by the preparation method of the porous hollow carbon nanospheres, and the preparation method comprises the following steps:
step S1: adding 0.25g of chitosan into 50mL of 1% acetic acid solution, putting into a round-bottom flask, magnetically stirring and dissolving, adding 0.1g of silicon dioxide into the acetic acid solution of chitosan, magnetically stirring and dispersing uniformly; and (3) weighing 0.05g of sodium tripolyphosphate, dissolving with 10mL of distilled water, placing in a constant pressure funnel, slowly dripping into the chitosan/silicon dioxide solution for 30min, and performing closed reaction for 10h under magnetic stirring in a water area at 55 ℃ to obtain a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid water phase system.
Step S2: mixing 3.4g of isooctyl palmitate, 3.4g of jojoba oil and 3.4g of hexadecyl-octadecanol, stirring and heating to 80 ℃, adding an emulsifier cetyl glucoside after uniform dissolution, and stirring and dissolving uniformly at 80 ℃ to obtain an oil phase; transferring the water phase system in the step S1 into a beaker, placing the beaker into a water area, heating to 80 ℃, adding the oil phase into the water phase system rapidly under stirring, stirring for 10min, homogenizing for 5min, and cooling to room temperature to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by grease;
step S3: placing the oil-in-water emulsion of the chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by the grease into a freeze dryer for freeze drying to obtain freeze-dried powder; adding the freeze-dried powder into absolute ethyl alcohol at the temperature of minus 10 ℃ to be uniformly dispersed, carrying out suction filtration and vacuum drying to obtain dry powder; placing the dry powder in a quartz boat, heating to 400 ℃ at a speed of 5 ℃/min under the protection of nitrogen, and preserving heat for 2 hours at the temperature; then heating to 1050 ℃ at a rate of 10 ℃, and preserving heat for 3 hours at the temperature; cooling to room temperature under the protection of nitrogen to obtain porous carbon nanospheres with silicon dioxide as a core;
step S4: and (3) placing the porous carbon nanospheres with the silicon dioxide as the core in hydrofluoric acid solution, stirring at room temperature for reaction for 12 hours, centrifugally separating, and washing to be neutral to obtain the porous hollow carbon nanospheres.
Example 3
The porous hollow carbon nanospheres are prepared by the preparation method of the porous hollow carbon nanospheres, and the preparation method comprises the following steps:
step S1: adding 0.25g of chitosan into 50mL of 1% acetic acid solution, putting into a round-bottom flask, magnetically stirring and dissolving, adding 0.1g of silicon dioxide into the acetic acid solution of chitosan, magnetically stirring and dispersing uniformly; and (3) weighing 0.05g of sodium tripolyphosphate, dissolving with 10mL of distilled water, placing in a constant pressure funnel, slowly dripping into the chitosan/silicon dioxide solution for 30min, and performing closed reaction for 10h under magnetic stirring in a water area at 45 ℃ to obtain a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid water phase system.
Step S2: mixing 3.4g of isooctyl palmitate, 3.4g of jojoba oil and 3.4g of hexadecyl-octadecanol, stirring and heating to 80 ℃, adding an emulsifier cetyl glucoside after uniform dissolution, and stirring and dissolving uniformly at 80 ℃ to obtain an oil phase; transferring the water phase system in the step S1 into a beaker, placing the beaker into a water area, heating to 80 ℃, adding the oil phase into the water phase system rapidly under stirring, stirring for 10min, homogenizing for 4min, and cooling to room temperature to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by grease;
step S3: placing the oil-in-water emulsion of the chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by the grease into a freeze dryer for freeze drying to obtain freeze-dried powder; adding the freeze-dried powder into absolute ethyl alcohol at the temperature of minus 10 ℃ to be uniformly dispersed, carrying out suction filtration and vacuum drying to obtain dry powder; placing the dry powder in a quartz boat, heating to 500 ℃ at a speed of 4 ℃/min under the protection of nitrogen, and preserving the temperature for 1.5h; heating to 950 ℃ at a rate of 8 ℃ and preserving heat for 4 hours at the temperature; cooling to room temperature under the protection of nitrogen to obtain porous carbon nanospheres with silicon dioxide as a core;
step S4: and (3) placing the porous carbon nanospheres with the silicon dioxide as the core in hydrofluoric acid solution, stirring at room temperature for reaction for 10 hours, centrifugally separating, and washing to be neutral to obtain the porous hollow carbon nanospheres.
Although the present disclosure is disclosed above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the disclosure.
Claims (10)
1. The preparation method of the porous hollow carbon nanospheres is characterized by comprising the following steps:
step S1: adding silicon dioxide into acetic acid solution of chitosan, stirring, dripping sodium tripolyphosphate aqueous solution, sealing, reacting, and magnetically stirring to obtain a chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid aqueous phase system;
step S2: mixing isooctyl palmitate, jojoba oil, sixteen-stearyl alcohol and an emulsifier, heating and stirring until the mixture is dissolved to obtain an oil phase, adding the oil phase into the chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid water phase system, and stirring to obtain an oil-in-water emulsion of a chitosan/sodium tripolyphosphate/silicon dioxide core material coated with grease;
step S3: the oil-in-water emulsion of the chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by the grease is subjected to freeze drying and high-temperature calcination to obtain the porous carbon nanospheres with the silicon dioxide as the core;
step S4: and placing the porous carbon nanospheres with the silicon dioxide as a core in hydrofluoric acid solution, stirring, centrifuging and washing to be neutral to obtain the porous hollow carbon nanospheres.
2. The method for preparing porous hollow carbon nanospheres according to claim 1, wherein in step S1, the magnetic stirring comprises: magnetically stirring the water area at 45-55 ℃; the time of the sealing reaction is 10 hours.
3. The method for preparing the porous hollow carbon nanospheres according to claim 1, wherein in step S2, after mixing isooctyl palmitate, jojoba oil, cetyl-stearyl alcohol and an emulsifier, heating and stirring until the mixture is dissolved to obtain an oil phase, comprising:
mixing the isooctyl palmitate, the jojoba oil and the hexadecyl-octadecanol, heating to 80 ℃, stirring until the mixture is uniformly dissolved, adding an emulsifying agent, and continuously stirring until the mixture is uniformly dissolved at the temperature of 80 ℃ to obtain an oil phase.
4. The method for preparing porous hollow carbon nanospheres according to claim 1, wherein in step S2, the emulsifier is cetyl glucoside.
5. The method for preparing the porous hollow carbon nanospheres according to claim 1, wherein in step S2, the oil phase is added into the aqueous phase system of chitosan/sodium tripolyphosphate/silica polymer colloid and stirred to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material coated with grease, and the method comprises the following steps:
under the condition that the water area temperature is 80 ℃, the oil phase is rapidly added into the chitosan/sodium tripolyphosphate/silicon dioxide polymer colloid water phase system while stirring, the mixture is stirred and homogenized, and the temperature is reduced to the room temperature, so that the oil-in-water emulsion of the chitosan/sodium tripolyphosphate/silicon dioxide core material wrapped by the grease is obtained.
6. The method of preparing porous hollow carbon nanospheres according to claim 5, wherein in step S2, the stirring time is 10min and the homogenizing time is 3-5min.
7. The method for preparing a porous hollow carbon nanosphere according to claim 1, wherein in step S3, the high-temperature calcination comprises: heating to 400-500 ℃ at a speed of 2-5 ℃/min under the protection of nitrogen, and preserving heat for 1-2h; then heating to 950-1050 ℃ at a rate of 5-10 ℃ and preserving heat for 3-4h.
8. The method for preparing porous hollow carbon nanospheres according to claim 1, wherein step S3 further comprises adding the oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material coated with the oil after freeze-drying into low-temperature absolute ethanol before high-temperature calcination, dispersing uniformly, filtering and vacuum drying.
9. The method for preparing porous hollow carbon nanospheres according to claim 8, wherein the temperature of the absolute ethanol in step S3 is-10 ℃.
10. The method for preparing porous hollow carbon nanospheres according to claim 1, wherein in step S4, the stirring time is 10 to 12 hours.
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