CN112076699A - Carbon composite silicon dioxide hollow core-shell material and preparation method thereof - Google Patents
Carbon composite silicon dioxide hollow core-shell material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a carbon composite silicon dioxide hollow core-shell material, which comprises the following steps: s1) mixing nano silicon dioxide, polyvinylpyrrolidone, pyrrole and a silane coupling agent in an alcohol-water solution, and then adding an initiator to carry out polymerization reaction to obtain a solid product; the temperature of the polymerization reaction is less than or equal to 35 ℃; s2) calcining the solid product at high temperature in a protective atmosphere, and etching in a mixed solution of ammonium fluoride and ammonia water to obtain the carbon composite silicon dioxide hollow core-shell material. Compared with the prior art, the method utilizes the combined action of hydrogen fluoride generated by slowly decomposing ammonium fluoride and ammonia water under the hydrothermal condition and the ammonia water, inhibits the etching degree of core silicon dioxide in the etching process, realizes the etching controllability, and further ensures that the composite material has porosity, larger specific surface area and core-shell structure.
Description
Technical Field
The invention belongs to the technical field of nano carbon materials, and particularly relates to a carbon composite silicon dioxide hollow core-shell material and a preparation method thereof.
Background
The influence of the shape structure of the material on the performance of the material is very important, namely the shape determines the property, and the preparation and the discovery of a novel material structure are always an important research direction. Core-shell materials are widely concerned by people due to their unique structural characteristics.
When the core shell is made of the same material, compared with the production of the material with the same quality, the consumption of raw materials can be greatly reduced, and more surface area and volume are increased. When the core shell is made of different materials, the properties of the inner material and the outer material can be combined to supplement the respective defects, and a certain synergistic effect can be achieved. For example, the carbon composite silica hollow core-shell material taking silica as a core and carbon material as a shell has a large specific surface area, and meanwhile, the introduction of carbon can further improve the electronic conductivity of the material, and has wide application prospects in the aspects of electro-catalysis, photocatalysis, lithium ion batteries, supercapacitors, oil-water separation and the like.
Preparation of core-shell structures a number of methods have been developed and the templating method is representative of the preparation of such structures. The template is used as a core, a coating layer is formed outside the template through chemical deposition, self-assembly, sol-gel and other means, and the template is removed through solvent dissolution or heat treatment to form a hollow structure. However, in the process of etching the template, the condition controllability is poor, and the template core is easily removed completely to directly form a complete hollow system, so that raw materials are wasted, and the complementary effect of the advantages of the two materials cannot be reflected.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a carbon composite silica hollow core-shell material and a preparation method thereof, wherein the preparation method has controllable etching.
The invention provides a preparation method of a carbon composite silicon dioxide hollow core-shell material, which comprises the following steps:
s1) mixing nano silicon dioxide, polyvinylpyrrolidone, pyrrole and a silane coupling agent in an alcohol-water solution, and then adding an initiator to carry out polymerization reaction to obtain a solid product; the temperature of the polymerization reaction is less than or equal to 35 ℃;
s2) calcining the solid product at high temperature in a protective atmosphere, and etching in a mixed solution of ammonium fluoride and ammonia water to obtain the carbon composite silicon dioxide hollow core-shell material.
Preferably, the step S1) is specifically:
S1A) mixing nano silicon dioxide and polyvinylpyrrolidone in an alcohol-water solution to obtain a mixture solution;
S1B) adding pyrrole and a silane coupling agent into the mixture solution, and then adding an initiator to carry out polymerization reaction to obtain a solid product.
Preferably, the mixing temperature in the step S1A) is 0-30 ℃; the mixing time is 30-90 min.
Preferably, the mass ratio of the nano silicon dioxide to the polyvinylpyrrolidone in the step S1) is (20-40): (6-9); the mass volume ratio of the nano silicon dioxide to the pyrrole is (400-800) mg: (0.5-1.5) ml; the volume ratio of the pyrrole to the silane coupling agent is (0.5-1.5): (0.05-0.2); the molar ratio of the pyrrole to the initiator is (0.007-0.02): (0.0004-0.0012); the mass-volume ratio of the solid product to the pyrrole is (200-600) mg: (0.5-1.5) ml.
Preferably, the ratio of the nano silicon dioxide to the alcohol aqueous solution is (400-1200) mg: (40-60) ml; the volume ratio of alcohol to water in the alcohol-water solution is (2-3): (2-3).
Preferably, the silane coupling agent is selected from triethoxysilane; the initiator is selected from potassium permanganate; the initiator is added in the form of an initiator solution; the concentration of the initiator in the initiator solution is 0.02-0.04 mol/L; and finishing adding the initiator solution within 20-60 min.
Preferably, the temperature of the polymerization reaction in the step S1) is 20-30 ℃; the polymerization reaction time in the step S1) is 6-12 h; the high-temperature calcination temperature is 600-1000 ℃; the high-temperature calcination is carried out for 1-6 h; the temperature rise rate of the high-temperature calcination is 2-5 ℃/min.
Preferably, the etching temperature of the step S3) is 100-180 ℃; the etching time is 5-20 h; the mass concentration of ammonium fluoride in the mixed seed solution is 2.5-25 mg/ml; the volume concentration of the ammonia water in the mixed solution is 15-50%.
The invention also provides the carbon composite silicon dioxide hollow core-shell material prepared by the method.
The invention provides a preparation method of a carbon composite silicon dioxide hollow core-shell material, which comprises the following steps: s1) mixing nano silicon dioxide, polyvinylpyrrolidone, pyrrole and a silane coupling agent in an alcohol-water solution, and then adding an initiator to carry out polymerization reaction to obtain a solid product; the temperature of the polymerization reaction is less than or equal to 35 ℃; s2) calcining the solid product at high temperature in a protective atmosphere, and etching in a mixed solution of ammonium fluoride and ammonia water to obtain the carbon composite silicon dioxide hollow core-shell material. Compared with the prior art, the method utilizes the combined action of hydrogen fluoride generated by slowly decomposing ammonium fluoride and ammonia water under the hydrothermal condition and the ammonia water, inhibits the etching degree of core silicon dioxide in the etching process, realizes the etching controllability, and further ensures that the composite material has porosity, larger specific surface area and core-shell structure.
Drawings
FIG. 1 is a scanning electron micrograph of a carbon composite silica hollow core-shell material obtained in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of the carbon composite silica hollow core-shell material obtained in example 1 of the present invention;
FIG. 3 is a TEM image of the carbon composite silica hollow core-shell material obtained in example 1 of the present invention;
FIG. 4 is a scanning electron micrograph of the carbon composite silica hollow core-shell material obtained in example 2 of the present invention;
FIG. 5 is a scanning electron micrograph of the carbon composite silica hollow core-shell material obtained in example 2 of the present invention;
FIG. 6 is a TEM image of the carbon composite silica hollow core-shell material obtained in example 2 of the present invention;
FIG. 7 is a TEM image of the carbon composite silica hollow core-shell material obtained in example 2 of the present invention;
FIG. 8 is a scanning electron micrograph of the carbon composite silica hollow core-shell material obtained in example 3 of the present invention;
FIG. 9 is a scanning electron micrograph of the carbon composite silica hollow core-shell material obtained in example 3 of the present invention;
FIG. 10 is a TEM image of the carbon composite silica hollow core-shell material obtained in example 3 of the present invention;
FIG. 11 is a TEM image of the carbon composite silica hollow core-shell material obtained in example 3 of the present invention;
FIG. 12 is a scanning electron micrograph of a highly nitrogen-doped nano hollow carbon sphere obtained in comparative example 1 of the present invention;
FIG. 13 is a TEM image of a highly N-doped hollow nanosphere obtained in comparative example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a carbon composite silicon dioxide hollow core-shell material, which comprises the following steps: s1) mixing nano silicon dioxide, polyvinylpyrrolidone, pyrrole and a silane coupling agent in an alcohol-water solution, and then adding an initiator to carry out polymerization reaction to obtain a solid product; the temperature of the polymerization reaction is less than or equal to 35 ℃; s2) calcining the solid product at high temperature in a protective atmosphere, and etching in a mixed solution of ammonium fluoride and ammonia water to obtain the carbon composite silicon dioxide hollow core-shell material.
In the present invention, the source of all raw materials is not particularly limited, and it may be commercially available or home-made.
In the present invention, the nano-silica is preferably prepared according to the following steps: mixing concentrated ammonia water, deionized water and absolute ethyl alcohol, then adding a mixed solution of tetraethoxysilane and absolute ethyl alcohol, and stirring for reaction to obtain the nano silicon dioxide.
Mixing concentrated ammonia water, deionized water and absolute ethyl alcohol; the mass concentration of the strong ammonia water is preferably 25%; the volume ratio of the concentrated ammonia water to the deionized water to the absolute ethyl alcohol is preferably (1.5-12): (0.5-4): (70-90), more preferably (3-10): (2-4): (70-80), and more preferably (4-8): (3-4): (70-75), most preferably 6: 4: 70; the mixing method is preferably stirring; the rotating speed of the stirring is preferably 100-500 rpm, more preferably 200-400 rpm, and further preferably 300 rpm; the mixing time is preferably 10-30 min, and more preferably 10-20 min; after mixing, a stable and uniform solution is obtained.
Then adding a mixed solution of tetraethoxysilane and absolute ethyl alcohol, and stirring for reaction; the volume ratio of the ethyl orthosilicate to the concentrated ammonia water is preferably (3-12): (1.5-12), more preferably (4-10): (3-10), more preferably (4-8): (4-8), most preferably 1: 1; the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol in the mixed solution is preferably (3-12): (20-40), more preferably (4-10): (30-40), and more preferably (4-8): (35-40), most preferably 6: 40; the adding mode of the mixed solution is preferably dropwise adding; the dripping time is preferably 60-120 min, more preferably 80-100 min, and further preferably 90 min; after the dropwise addition of the mixed solution is finished, preferably continuously stirring for reaction; the stirring reaction is preferably carried out at normal temperature; the stirring reaction time is preferably 1-6 h, more preferably 3-5 h, and further preferably 4 h; the rotation speed of the stirring reaction is preferably 200-800 rpm, more preferably 400-600 rpm, and still more preferably 500 rpm.
After the reaction is finished, preferably centrifuging, washing and drying to obtain nano silicon dioxide; the centrifugal speed is preferably 8000-10000 rpm, more preferably 8000-9000 rpm; the centrifugation time is preferably 10-20 min, and more preferably 15-20 min; the washing is preferably ethanol; the washing frequency is preferably 2-3 times; the drying is preferably freeze drying; the temperature of the freeze drying is preferably-80 ℃ to-20 ℃, more preferably-60 ℃ to-40 ℃, and further preferably-50 ℃; the freeze drying time is preferably 8-20 hours, more preferably 8-15 hours, and further preferably 10-12 hours.
Mixing nano silicon dioxide, polyvinylpyrrolidone, pyrrole and a silane coupling agent in an alcohol-water solution; preferably, the nano silicon dioxide and the polyvinylpyrrolidone are mixed in an alcohol-water solution to obtain a mixture solution; then adding pyrrole and a silane coupling agent into the mixture solution; the mass ratio of the nano silicon dioxide to the polyvinylpyrrolidone is preferably (20-40): (6-9), more preferably (30-40): (7-9), and more preferably 40: (8-9), most preferably 40: 9; the preferable proportion of the nano silicon dioxide to the alcohol water solution is (400-800) mg: (40-60) ml, more preferably (600-800) mg: (50-60) ml, more preferably 800 mg: 60 ml; the volume ratio of alcohol to water in the alcohol-water solution is preferably (2-3): (2-3), more preferably 1: 1; the alcohol in the alcohol aqueous solution is preferably ethanol; the nano silicon dioxide and the polyvinylpyrrolidone are preferably ultrasonically dispersed in an alcohol-water solution; the power of the ultrasonic wave is preferably 100-500W, more preferably 100-400W, and further preferably 200-300W; the mixing temperature is preferably 0-30 ℃, more preferably 0-10 ℃, and further preferably 0-4 ℃; the mixing time is preferably 30-90 min, more preferably 30-60 min, and further preferably 30-40 min; in the invention, the mixture solution after ultrasonic treatment is preferably continuously stirred in a water bath at 0-30 ℃, and then pyrrole and a silane coupling agent are added into the mixture solution; the stirring time is preferably 10-30 min, and more preferably 20 min; the mass volume ratio of the nano silicon dioxide to the pyrrole is preferably (400-800) mg: (0.5 to 1.5) ml, more preferably (600 to 800) mg: (0.5 to 1.5) ml, more preferably (700 to 800) mg: (0.8-1.2) ml, most preferably 800 mg: 1 ml; the volume ratio of the pyrrole to the silane coupling agent is preferably (0.5-1.5): (0.05-0.2), more preferably (0.5-1.5): (0.1-0.2), and more preferably (0.8-1.2): 0.15, most preferably 1: 0.15; the silane coupling agent is preferably triethoxysilane.
After adding pyrrole and silane coupling agent, preferably stirring uniformly, and then adding initiator to carry out polymerization reaction; the molar ratio of the pyrrole to the initiator is preferably (0.007-0.02): (0.0004 to 0.0012), more preferably (0.008 to 0.015): (0.0005 to 0.001), more preferably (0.01 to 0.015): (0.0005 to 0.001), most preferably 0.014: 0.0009; the initiator is preferably a peroxide initiator, more preferably potassium persulfate; the initiator is preferably added in the form of an initiator solution; the concentration of the initiator in the initiator solution is preferably 0.02-0.04 mol/L, and more preferably 0.03 mol/L; the initiator solution is preferably added within 20-60 min, more preferably within 20-50 min, still more preferably within 20-40 min, and most preferably within 30 min; the temperature of the polymerization reaction is preferably 20-30 ℃, and more preferably 25 ℃; the time of the polymerization reaction is preferably 6-12 hours, and more preferably 10-12 hours.
After the polymerization reaction is finished, preferably centrifuging, washing and drying to obtain a solid product; the centrifugal speed is preferably 5000-8000 rpm, and more preferably 6000-8000 rpm; the centrifugation time is preferably 15-30 min, and more preferably 20-25 min; the washing is preferably ethanol; the drying is preferably freeze drying; the temperature of the freeze drying is preferably-80 ℃ to-20 ℃, more preferably-60 ℃ to-40 ℃, and further preferably-50 ℃; the freeze drying time is preferably 8-20 hours, more preferably 8-15 hours, and further preferably 10-12 hours.
Calcining the solid product at high temperature in a protective atmosphere; the protective atmosphere is not particularly limited as long as it is known to those skilled in the art, and nitrogen is preferred in the present invention; the high-temperature calcination temperature is preferably 600-1000 ℃, more preferably 600-900 ℃, more preferably 600-800 ℃ and most preferably 800 ℃; the heat preservation time of the high-temperature calcination is preferably 1-6 h, and more preferably 1-4 h; the heating rate of the high-temperature calcination is preferably 2-5 ℃/min.
After high-temperature calcination, etching in a mixed solution of ammonium fluoride and ammonia water; the mass concentration of the ammonium fluoride in the mixed solution is preferably 2.5-25 mg/ml, more preferably 5-20 mg/ml, even more preferably 5-15 mg/ml, and most preferably 5-10 mg/ml; the volume concentration of the ammonia water in the mixed solution is preferably 15-50%, and more preferably 25-50%; the etching temperature is preferably 100-180 ℃, more preferably 120-160 ℃, and further preferably 150 ℃; the etching time of the solution is preferably 5-20 hours, and more preferably 10-15 hours.
After etching, preferably washing and drying to obtain the carbon composite silicon dioxide hollow core-shell material; deionized water and ethanol are preferably adopted for washing; the drying is preferably freeze drying; the temperature of the freeze drying is preferably-80 ℃ to-20 ℃, more preferably-60 ℃ to-40 ℃, and further preferably-50 ℃; the freeze drying time is preferably 8-20 hours, more preferably 8-15 hours, and further preferably 10-12 hours.
The carbon composite silicon dioxide hollow core-shell material is polymerized under the low temperature condition, so that the obtained carbon composite silicon dioxide hollow core-shell material has regular shape, larger specific surface area and higher nitrogen content, and simultaneously, the controllability of etching is realized by utilizing the combined action of hydrogen fluoride generated by slowly decomposing ammonium fluoride and ammonia water under the hydrothermal condition and the ammonia water, so that the material has porosity, larger specific surface area and core-shell structure.
The invention also provides the carbon composite silicon dioxide hollow core-shell material prepared by the method.
In order to further illustrate the present invention, the following describes a carbon composite silica hollow core-shell material and a preparation method thereof in detail with reference to examples.
The reagents used in the following examples are all commercially available.
Example 1
Firstly, mixing 6mL of strong ammonia water (25%), 4mL of deionized water and 70mL of absolute ethyl alcohol, and then placing the mixture in a three-neck flask; placing the mixed solution in a normal temperature water bath, and magnetically stirring for 10min at 300 rpm; and adding a mixed solution of 6mL of ethyl orthosilicate and 40mL of ethanol into the constant-pressure funnel, slowly dropwise adding the mixed solution into the three-neck flask, and continuing to react for 4 hours after the dropwise adding is finished for 90min, wherein the preparation of the silicon dioxide spheres is finished. And then, centrifugally separating the solution after the reaction is finished by a high-speed centrifuge at 8000rpm for 20min, washing the solution for 2 times by using ethanol, and then, freeze-drying the solution at the temperature of minus 50 ℃ for 12h to obtain the solid silicon dioxide spheres.
Ultrasonically dispersing 800mg of solid silicon dioxide spheres and 180mg of polyvinylpyrrolidone in 60mL of ethanol water solution (volume ratio is 1: 1), wherein the ultrasonic dispersion power is 200W, and the ultrasonic dispersion time is 30 min; placing the dispersed solution in ice-water bath at 0 ℃ and continuously stirring for 20min, and adding 1.0mL of pyrrole monomer and 0.15mL of KH 550; and then, dropwise adding 30mL of 0.03mol/L high potassium sulfate solution into the mixed solution for 30min, then continuously stirring and fully reacting for 12h (the reaction temperature is 25 ℃), centrifuging at 8000rpm for 20min, washing with ethanol, and freeze-drying at-50 ℃ for 12h to obtain a black solid product.
And finally, heating the solid product to 800 ℃ at the speed of 2 ℃/min under nitrogen atmosphere, keeping the temperature for 4 hours, calcining to obtain a product, placing the product into 20mL of mixed solution (the mass of ammonium fluoride in the mixed solution is 200mg, and the volume of an ammonia water solution is 5mL), etching for 5 hours at the temperature of 100 ℃, washing the final solid product with ethanol, and freeze-drying at the temperature of-50 ℃ for 12 hours to obtain the carbon composite silicon dioxide hollow core-shell material.
Scanning electron microscopy was used to analyze the carbon composite silica hollow core-shell material obtained in example 1, and scanning electron micrographs thereof are shown in fig. 1 and 2.
The carbon composite silica hollow core-shell material obtained in example 1 was analyzed by a transmission electron microscope, and a transmission electron micrograph thereof is shown in fig. 3.
Example 2
Firstly, mixing 6mL of strong ammonia water (25%), 4mL of deionized water and 70mL of absolute ethyl alcohol, and then placing the mixture in a three-neck flask; placing the mixed solution in a normal temperature water bath, and magnetically stirring for 10min at 300 rpm; and adding a mixed solution of 6mL of ethyl orthosilicate and 40mL of ethanol into the constant-pressure funnel, slowly dropwise adding the mixed solution into the three-neck flask, and continuing to react for 4 hours after the dropwise adding is finished for 90min, wherein the preparation of the silicon dioxide spheres is finished. And then, centrifugally separating the solution after the reaction is finished by a high-speed centrifuge at 8000rpm for 20min, washing the solution for 2 times by using ethanol, and then, freeze-drying the solution at the temperature of minus 50 ℃ for 12h to obtain the solid silicon dioxide spheres.
Ultrasonically dispersing 800mg of solid silicon dioxide spheres and 180mg of polyvinylpyrrolidone in 60mL of ethanol water solution (volume ratio is 1: 1), wherein the ultrasonic dispersion power is 200W, and the ultrasonic dispersion time is 30 min; placing the dispersed solution in ice-water bath at 0 ℃ and continuously stirring for 20min, and adding 1.0mL of pyrrole monomer and 0.15mL of KH 550; and then, dropwise adding 30mL of 0.03mol/L high potassium sulfate solution into the mixed solution for 30min, then continuously stirring and fully reacting for 12h (the reaction temperature is 25 ℃), centrifuging at 8000rpm for 20min, washing with ethanol, and freeze-drying at-50 ℃ for 12h to obtain a black solid product.
And finally, heating the solid product to 800 ℃ at the speed of 2 ℃/min under nitrogen atmosphere, keeping the temperature for 4 hours, calcining to obtain a product, placing the product into 20mL of mixed solution (the mass of ammonium fluoride in the mixed solution is 200mg, and the volume of an ammonia water solution is 5mL), etching at 150 ℃ for 10 hours, washing the final solid product with ethanol, and freeze-drying at-50 ℃ for 12 hours to obtain the carbon composite silicon dioxide hollow core-shell material.
Scanning electron microscopy was used to analyze the carbon composite silica hollow core-shell material obtained in example 2, and scanning electron micrographs thereof are shown in fig. 4 and 5.
The carbon composite silica hollow core-shell material obtained in example 2 was analyzed by a transmission electron microscope, and transmission electron micrographs thereof were obtained as shown in fig. 6 and 7.
Example 3
Firstly, mixing 6mL of strong ammonia water (25%), 4mL of deionized water and 70mL of absolute ethyl alcohol, and then placing the mixture in a three-neck flask; placing the mixed solution in a normal temperature water bath, and magnetically stirring for 10min at 300 rpm; and adding a mixed solution of 6mL of ethyl orthosilicate and 40mL of ethanol into the constant-pressure funnel, slowly dropwise adding the mixed solution into the three-neck flask, and continuing to react for 4 hours after the dropwise adding is finished for 90min, wherein the preparation of the silicon dioxide spheres is finished. And then, centrifugally separating the solution after the reaction is finished by a high-speed centrifuge at 8000rpm for 20min, washing the solution for 2 times by using ethanol, and then, freeze-drying the solution at the temperature of minus 50 ℃ for 12h to obtain the solid silicon dioxide spheres.
Ultrasonically dispersing 800mg of solid silicon dioxide spheres and 180mg of polyvinylpyrrolidone in 60mL of ethanol water solution (volume ratio is 1: 1), wherein the ultrasonic dispersion power is 200W, and the ultrasonic dispersion time is 30 min; placing the dispersed solution in ice-water bath at 0 ℃ and continuously stirring for 20min, and adding 1.0mL of pyrrole monomer and 0.15mL of KH 550; and then, dropwise adding 30mL of 0.03mol/L high potassium sulfate solution into the mixed solution for 30min, then continuously stirring and fully reacting for 12h (the reaction temperature is 25 ℃), centrifuging at 8000rpm for 20min, washing with ethanol, and freeze-drying at-50 ℃ for 12h to obtain a black solid product.
And finally, heating the solid product to 800 ℃ at the speed of 2 ℃/min under nitrogen atmosphere, keeping the temperature for 4 hours, calcining to obtain a product, placing the product into 20mL of mixed solution (the mass of ammonium fluoride in the mixed solution is 200mg, and the volume of an ammonia water solution is 5mL), etching for 15 hours at 180 ℃, washing the final solid product with ethanol, and freeze-drying at-50 ℃ for 12 hours to obtain the carbon composite silicon dioxide hollow core-shell material.
Scanning electron microscopy was used to analyze the carbon composite silica hollow core-shell material obtained in example 3, and scanning electron micrographs thereof are shown in fig. 8 and 9.
The carbon composite silica hollow core-shell material obtained in example 3 was analyzed by a transmission electron microscope, and transmission electron micrographs thereof were obtained as shown in fig. 10 and 11.
Comparative example 1
Firstly, mixing 6mL of strong ammonia water (25%), 4mL of deionized water and 70mL of absolute ethyl alcohol, and then placing the mixture in a three-neck flask; placing the mixed solution in a normal temperature water bath, and magnetically stirring for 10min at 300 rpm; and adding a mixed solution of 6mL of ethyl orthosilicate and 40mL of ethanol into the constant-pressure funnel, slowly dropwise adding the mixed solution into the three-neck flask, and continuing to react for 4 hours after the dropwise adding is finished for 90min, wherein the preparation of the silicon dioxide spheres is finished. Then, centrifugally separating the solution after the reaction for 20min by using a high-speed centrifuge at 8000rpm, washing, and ultrasonically dispersing 1200mg of solid silicon dioxide spheres and 180mg of polyvinylpyrrolidone in 60ml of ethanol water solution (volume ratio is 1: 1), wherein the ultrasonic dispersion power is 200W, and the time is 30 min; placing the dispersed solution in a water bath at 30 ℃ and continuously stirring for 20min, and adding 0.5mL of pyrrole monomer and 0.15mL of KH 550; 30mL of high potassium sulfate solution (concentration 0.03mol/L) is added, the mixture is continuously stirred and fully reacted for 12h at 50 ℃, and the black solid product is obtained after the mixture is centrifuged at 8000rpm for 20min, washed and dried. And finally, heating the solid product to 800 ℃ at the speed of 2 ℃/min under nitrogen atmosphere, calcining for 2 hours at constant temperature, placing the product into 10ml of 1mol/L sodium hydroxide solution, etching for 1 hour at 80 ℃, washing the final solid product with ethanol, and freeze-drying for 12 hours at 50 ℃ to obtain the high-nitrogen doped nano hollow carbon spheres.
The high nitrogen-doped nano hollow carbon spheres obtained in comparative example 1 were analyzed by a scanning electron microscope, and a scanning electron micrograph thereof is shown in fig. 12.
The high nitrogen-doped nano hollow carbon spheres obtained in comparative example 1 were analyzed by a transmission electron microscope, and a transmission electron micrograph thereof is shown in fig. 13.
Claims (9)
1. A preparation method of a carbon composite silicon dioxide hollow core-shell material is characterized by comprising the following steps:
s1) mixing nano silicon dioxide, polyvinylpyrrolidone, pyrrole and a silane coupling agent in an alcohol-water solution, and then adding an initiator to carry out polymerization reaction to obtain a solid product; the temperature of the polymerization reaction is less than or equal to 35 ℃;
s2) calcining the solid product at high temperature in a protective atmosphere, and etching in a mixed solution of ammonium fluoride and ammonia water to obtain the carbon composite silicon dioxide hollow core-shell material.
2. The preparation method according to claim 1, wherein the step S1) is specifically:
S1A) mixing nano silicon dioxide and polyvinylpyrrolidone in an alcohol-water solution to obtain a mixture solution;
S1B) adding pyrrole and a silane coupling agent into the mixture solution, and then adding an initiator to carry out polymerization reaction to obtain a solid product.
3. The method according to claim 2, wherein the mixing temperature in the step S1A) is 0-30 ℃; the mixing time is 30-90 min.
4. The preparation method according to claim 1, wherein the mass ratio of the nano silica to the polyvinylpyrrolidone in the step S1) is (20-40): (6-9); the mass volume ratio of the nano silicon dioxide to the pyrrole is (400-800) mg: (0.5-1.5) ml; the volume ratio of the pyrrole to the silane coupling agent is (0.5-1.5): (0.05-0.2); the molar ratio of the pyrrole to the initiator is (0.007-0.02): (0.0004-0.0012); the mass-volume ratio of the solid product to the pyrrole is (200-600) mg: (0.5-1.5) ml.
5. The preparation method according to claim 1, wherein the ratio of the nano silica to the alcohol aqueous solution is (400-1200) mg: (40-60) ml; the volume ratio of alcohol to water in the alcohol-water solution is (2-3): (2-3).
6. The method according to claim 1, wherein the silane coupling agent is selected from the group consisting of triethoxysilane; the initiator is selected from potassium permanganate; the initiator is added in the form of an initiator solution; the concentration of the initiator in the initiator solution is 0.02-0.04 mol/L; and finishing adding the initiator solution within 20-60 min.
7. The preparation method according to claim 1, wherein the temperature of the polymerization reaction in the step S1) is 20 ℃ to 30 ℃; the polymerization reaction time in the step S1) is 6-12 h; the high-temperature calcination temperature is 600-1000 ℃; the high-temperature calcination is carried out for 1-6 h; the temperature rise rate of the high-temperature calcination is 2-5 ℃/min.
8. The preparation method according to claim 1, wherein the temperature of the etching in the step S3) is 100-180 ℃; the etching time is 5-20 h; the mass concentration of ammonium fluoride in the mixed seed solution is 2.5-25 mg/ml; the volume concentration of the ammonia water in the mixed solution is 15-50%.
9. The carbon composite silica hollow core-shell material prepared by the preparation method of any one of claims 1 to 8.
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| CN115121224A (en) * | 2022-08-05 | 2022-09-30 | 广东省建工设计院有限公司 | Sludge carbon biological filler with core-shell structure and preparation method and application thereof |
| CN115873425A (en) * | 2022-12-27 | 2023-03-31 | 江苏臻远生物科技有限公司 | Preparation method of nanoparticles for enhancing laser marking effect of black master batch |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664936A (en) * | 2016-01-07 | 2016-06-15 | 上海工程技术大学 | Method for preparing nano composite material having core-shell structure with dopamine as carbon source |
| CN107001045A (en) * | 2015-10-26 | 2017-08-01 | 沙特基础工业全球技术公司 | The preparation of CNT shell material |
-
2020
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107001045A (en) * | 2015-10-26 | 2017-08-01 | 沙特基础工业全球技术公司 | The preparation of CNT shell material |
| CN105664936A (en) * | 2016-01-07 | 2016-06-15 | 上海工程技术大学 | Method for preparing nano composite material having core-shell structure with dopamine as carbon source |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115121224A (en) * | 2022-08-05 | 2022-09-30 | 广东省建工设计院有限公司 | Sludge carbon biological filler with core-shell structure and preparation method and application thereof |
| CN115873425A (en) * | 2022-12-27 | 2023-03-31 | 江苏臻远生物科技有限公司 | Preparation method of nanoparticles for enhancing laser marking effect of black master batch |
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