CN114590795B - Core-shell special-shaped porous carbon sphere and preparation method thereof - Google Patents

Core-shell special-shaped porous carbon sphere and preparation method thereof Download PDF

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CN114590795B
CN114590795B CN202210331436.3A CN202210331436A CN114590795B CN 114590795 B CN114590795 B CN 114590795B CN 202210331436 A CN202210331436 A CN 202210331436A CN 114590795 B CN114590795 B CN 114590795B
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core
shell
porous carbon
shaped porous
carbon sphere
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CN114590795A (en
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司银松
蔡依池
杨紫琦
李魁
钱丹妮
杜加信
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Zhejiang Sci Tech University ZSTU
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a core-shell special-shaped porous carbon sphere and a preparation method thereof. Dissolving surfactant in alcohol/water/NH 4 Adding a silicon source and a pore-expanding agent into an OH system under the condition of rapid stirring, and reacting to obtain radial porous SiO 2 A microsphere; then go to the opposite directionAdding a carbon source into the reaction system, calcining the product obtained after the reaction under the protection of inert gas, and etching silicon dioxide to obtain the core-shell irregularly-shaped porous carbon spheres. The core of the core-shell special-shaped porous carbon sphere is a radial mesoporous microsphere, the shell is a hollow microsphere, and the mesoporous aperture of the core and the shell thickness of the shell can be controlled and regulated. The core and the shell of the core-shell special-shaped porous carbon sphere are tightly connected, the advantages of the porous microspheres and the hollow microspheres are achieved, and the core-shell special-shaped porous carbon sphere has wide application prospects in the fields of firm load of guest substances, lithium ion batteries, electromagnetic wave absorption and the like.

Description

Core-shell special-shaped porous carbon sphere and preparation method thereof
Technical Field
The invention relates to the field of nano carbon sphere preparation, in particular to a core-shell special-shaped porous carbon sphere and a preparation method thereof.
Background
Porous materials can be classified into microporous, mesoporous, macroporous materials. Porous microspheres have a larger specific surface area than solid microspheres, and can provide more adsorption sites and reaction sites. For mesoporous carbon materials, the main preparation methods at present mainly comprise a hard template method, a soft template method, hydrothermal carbonization, emulsion polymerization and the like. The hard template method is a common method for preparing carbon spheres, and the morphology of the mesoporous carbon spheres depends on the morphology of a template agent and is easy to regulate and control. Silica is often used as a template to prepare carbon spheres. The mesoporous carbon sphere has the excellent characteristics of porous materials and carbon materials, and has the advantages of large specific surface area, large pore volume, low density, good heat conduction, electric conduction, chemical and mechanical stability and the like, and has great application potential in the aspects of adsorption in the processes of catalysts, sensors, separation and the like.
The porous structure in the mesoporous carbon sphere enables the mesoporous carbon sphere to have moderate dielectric constant, most electromagnetic waves can enter the mesoporous carbon sphere, more interface polarization loss is manufactured, electromagnetic wave absorption can be enhanced, and the impedance matching performance of the carbon material is improved. Because of these excellent physical properties of mesoporous carbon spheres, and lightweight, they are widely used in the field of electromagnetic wave absorption and shielding. However, the existing preparation method of the porous carbon spheres has some problems, such as difficult adjustment of pore diameters, difficult control of morphology and the like, so that the development of the porous carbon spheres is limited.
Disclosure of Invention
The invention aims to provide a preparation method of a core-shell special-shaped porous carbon sphere, and NH can be adjusted 4 The pore size of the radial mesoporous of the inner core is adjusted by the value of OH/paraxylene, and the thickness of the outer shell layer is regulated and controlled by controlling the amount of the added carbon source, so that the porous carbon spheres with different shell layer thicknesses are obtained.
The invention firstly provides a preparation method of a core-shell special-shaped porous carbon sphere, which comprises the following steps:
step 1, preparing alcohol and water into a mixed solution, adding a surfactant and ammonia water into the mixed solution, stirring at room temperature, adding a silicon source into the solution, stirring for a certain time, and adding paraxylene to react for a period of time to obtain radial mesoporous SiO 2 A microsphere;
step 2, adding a carbon source into the reaction system, stirring, fully reacting, centrifuging, washing, freeze-drying, drying and calcining the obtained solution to obtain SiO with the inner core 2 Is a nano carbon sphere;
step 3, siO in the nano carbon spheres in the step 2 is treated 2 And etching to obtain the porous carbon spheres with special core shells.
As a preferred embodiment of the present invention, in the step 1, the surfactant is one or more of cetyltrimethylammonium bromide (CTAB) or cetyltrimethylammonium chloride (CTAC).
As a preferable scheme of the invention, the silicon source is one or more of tetraethyl silicate, tetrapropyl silicate and silicon tetrachloride.
As a preferable scheme of the invention, in the step 1, the volume ratio of the alcohol to the water is 0.5-0.8:1; volume ratio of ammonia water to alcohol: 0.01-0.02:1, a step of; the volume ratio of the silicon source to the alcohol is 0.06-0.1:1; the reaction time is 2-4 h; the stirring speed is 600-800 rpm; adding paraxylene after adding silicon source for 2-10 min; the volume ratio of the ammonia water to the paraxylene is 0.15-0.3:1; the mass percentage of ammonia in the ammonia water is 25-28%.
As a preferred embodiment of the present invention, in the step 1, the alcohol is one or more of ethanol, methanol, n-propanol, isopropanol, ethylene glycol, benzyl alcohol, butanol, amyl alcohol, hexanol, octanol, and 2-methyl-1-propanol.
In the step 2, the mass ratio of the added carbon source to the SiO2 microsphere is more than 2; the reaction time of the system is 1-48 h.
In the preferred embodiment of the present invention, in the step 2, the carbon source is one of dopamine hydrochloride or phenolic resin.
The invention also provides the porous carbon sphere prepared by the method, wherein the inner core of the porous carbon sphere is a radial mesoporous carbon sphere, the outer shell of the porous carbon sphere is a hollow microsphere, the inner core of the porous carbon sphere is tightly connected with the outer shell, and the mesoporous aperture of the inner core and the shell thickness of the outer shell can be controlled and regulated. The particle size of the porous carbon sphere is 400-600 nm, and the thickness of the outer shell layer is more than 20nm.
The invention uses radial hole-shaped SiO 2 The microsphere is used as a template, and the surface of the microsphere is coated with a carbon layer to obtain the porous carbon sphere with novel core-shell special shape. Paraxylene is taken as a swelling agent to enter CTAB micelle and form SiO together with the CTAB micelle 2 Particle binding by adjusting NH 4 OH and paraxylene volume ratio, and realizes the regulation and control of microsphere morphology. In an alternative embodiment, dopamine hydrochloride is used as the carbon source, hydrolyzed and formed on SiO 2 The surface self-polymerizes to form polydopamine microspheres, and the surfaces of the polydopamine microspheres are coated with a layer of shell after deposition. The thickness of the shell layer is regulated by regulating the consumption and the reaction time of dopamine hydrochloride. The polydopamine has good shape retention property and high calcining carbonization rate, and is a good carbon source. Finally, etching the microspheres obtained after calcination to obtain the porous carbon spheres with special core-shell shapes.
The porous carbon sphere prepared by the invention has the advantages that the inner core is a radial mesoporous carbon sphere, the outer shell is a hollow microsphere, the inner core is tightly connected with the outer shell, and the mesoporous aperture of the inner core and the shell thickness of the outer shell can be controlled and regulated. The particle size of the porous carbon sphere is 400-500 nm, and the thickness of the outer shell layer is more than 20nm. The porous carbon sphere has the advantages of both porous microspheres and hollow microspheres, and because the shell is tightly connected with the porous hole wall, more conductive paths or electromagnetic loss paths can be formed, and better conductivity or electromagnetic shielding effect is shown; the inner hole wall also plays a role of supporting the shell, so that the whole structure of the microsphere is firmer, mechanical damage to the microsphere caused by external pressure is better resisted, and due to the larger specific surface area and pores of the inner porous structure, a buffer space is provided for volume changes of some guest substances (such as volume expansion of active substances before and after repeated charging of a lithium battery, and the like), so that the guest molecules and substances can be better adsorbed in the porous, and meanwhile, the shell can prevent adsorbed and loaded substances from escaping; in summary, the porous carbon sphere has excellent conductivity, stability and adsorptivity, and has wide application prospects in the fields of firm load of guest substances, lithium ion batteries, electromagnetic wave absorption and the like.
The synthesis method provided by the invention is simple and easy to operate, and the prepared porous carbon sphere has special core-shell shape, good sphericity and novel structure. The radial mesoporous aperture of the inner core and the shell thickness of the outer shell are easy to regulate and control. The outer shell layer ensures that the porous carbon sphere has the capability of firmly encapsulating objects, and the radial mesoporous structure and the outer shell layer can reflect and scatter electromagnetic waves for multiple times, so that the carbon sphere has better wave absorbing performance.
Drawings
FIG. 1 is a TEM image of the sample obtained in example 1;
FIG. 2 is a TEM image of the sample obtained in example 2;
FIG. 3 is a TEM image of the sample obtained in example 3.
Detailed description of the preferred embodiments
The present invention will be described in detail with reference to the following detailed description and the accompanying drawings. It should be understood that the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, after reading the present disclosure, those skilled in the art may make various changes or modifications to the present disclosure, and these equivalents also fall within the scope of the present application as defined in the appended claims.
Example 1
40g of ethanol and 80g of water were mixed to prepare a solution. To this mixed solution were added 0.8g of CTAB powder and 0.6mL of NH 4 OH, mechanically stirred at room temperature for 30min at 600rpm. 2.4mL of tetraethyl silicate is added into the solution, 4.0mL of paraxylene is added after 2min, and the reaction is carried out for 2h, thus preparing the radial mesoporous SiO 2 And (3) microspheres.
The prepared mesoporous SiO 2 To the microsphere system, 0.75g of dopamine hydrochloride was added and stirred to react well for 24 hours at a stirring speed of 800rpm. The reaction solution was centrifuged and washed, and the resulting powder was lyophilized in a freeze dryer and dried in a vacuum oven at 40 ℃. And (3) placing the powder into a tube furnace to be calcined under the nitrogen atmosphere, and performing carbonization treatment. The calcination is that the calcination temperature is gradually increased from room temperature to 350 ℃, the temperature rising speed is 5 ℃/min, the temperature is kept at 350 ℃ for 1h, the temperature is increased to 800 ℃ at the same temperature rising speed, the temperature is kept at 800 ℃ for 2h, and the black powder with SiO as the inner core is obtained 2 Is a nano carbon sphere.
Soaking the composite microsphere in ammonium bifluoride solution to eliminate SiO 2 Centrifuging and washing, and drying in a vacuum oven at 40 ℃ to obtain the nano carbon spheres with radial inner core mesopores and a layer of shell wrapped outside.
Fig. 1 is a transmission electron microscope image of the nanocarbon ball prepared in example 1. As can be seen from fig. 1, the average particle size of the nanocarbon ball prepared in this example is 400nm, the average thickness of the outer shell layer is 20nm, and the inner pore canal is radial.
Example 2
50g of ethanol and 80g of water were mixed to prepare a solution. To this mixed solution was added 0.8g CTAC powder and 1.2mL NH 4 OH, mechanically stirred at room temperature for 30min at 800rpm. 3.0mL of tetrapropyl silicate is added into the solution, 4.0mL of paraxylene is added after 10min, and the reaction is carried out for 4h, thus preparing the radial mesoporous SiO 2 And (3) microspheres.
The prepared mesoporous SiO 2 Adding 0.9g of dopamine hydrochloride into the microsphere system, stirring and fillingThe reaction was carried out for 48 hours with stirring at 800rpm. The reaction solution was centrifuged and washed, and the resulting powder was lyophilized in a freeze dryer and dried in a vacuum oven at 40 ℃. And (3) placing the powder into a tube furnace to be calcined under the nitrogen atmosphere, and performing carbonization treatment. The calcination is that the calcination temperature is gradually increased from room temperature to 350 ℃, the temperature rising speed is 5 ℃/min, the temperature is kept at 350 ℃ for 1h, the temperature is increased to 800 ℃ at the same temperature rising speed, the temperature is kept at 800 ℃ for 2h, and the black powder with SiO as the inner core is obtained 2 Is a nano carbon sphere.
Soaking the composite microsphere in ammonium bifluoride solution to eliminate SiO 2 Centrifuging and washing, and drying in a vacuum oven at 40 ℃ to obtain the nano carbon spheres with radial inner core mesopores and a layer of shell wrapped outside.
Fig. 2 is a transmission electron microscope image of the nanocarbon ball prepared in example 2. As can be seen from fig. 2, the average particle size of the nanocarbon ball prepared in this example is 500nm, the average thickness of the outer shell layer is 50nm, and the inner pore canal is radial.
Example 3 (counter example)
In contrast to example 1, the amount of dopamine hydrochloride is reduced and the other conditions are unchanged.
40g of ethanol and 80g of water were mixed to prepare a solution. To this mixed solution were added 0.8g of CTAB powder and 0.6mL of NH 4 OH, mechanically stirred at room temperature for 30min at 600rpm. 2.4mL of tetraethyl silicate is added into the solution, 4.0mL of paraxylene is added after 2min, and the reaction is carried out for 2h, thus preparing the radial mesoporous SiO 2 And (3) microspheres.
The prepared mesoporous SiO 2 To the microsphere system, 0.6g of dopamine hydrochloride was added and stirred to react well for 24 hours at a stirring speed of 800rpm. The reaction solution was centrifuged and washed, and the resulting powder was lyophilized in a freeze dryer and dried in a vacuum oven at 40 ℃. And (3) placing the powder into a tube furnace to be calcined under the nitrogen atmosphere, and performing carbonization treatment. The calcination means that the calcination temperature is gradually increased from room temperature to 350 ℃, the temperature rising speed is 5 ℃/min, the calcination is kept at 350 ℃ for 1h, the calcination temperature is increased to 800 ℃ at the same temperature rising speed, and the calcination is kept at 800 ℃ for 2h, so that the black material is obtainedThe color powder is SiO as the inner core 2 Is a nano carbon sphere.
Soaking the composite microsphere in ammonium bifluoride solution to eliminate SiO 2 Centrifuging and washing, and drying in a vacuum oven at 40 ℃ to obtain the nano carbon spheres.
Fig. 3 is a transmission electron microscope image of the nanocarbon ball prepared in example 3. As can be seen from fig. 3, the average particle size of the nanocarbon ball prepared in this example is 400nm, and the outside is not coated with a carbon shell.
The foregoing examples are provided to illustrate the present invention and are described in more detail, but are not to be construed as limiting the scope of the invention. It should be noted that several variations and modifications can be made without departing from the inventive concept, which fall within the scope of the present invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.

Claims (7)

1. The preparation method of the core-shell special-shaped porous carbon sphere is characterized by comprising the following steps of:
step 1, preparing alcohol and water into a mixed solution, adding a surfactant and ammonia water into the mixed solution, stirring at room temperature, adding a silicon source into the solution, stirring for a certain time, and adding paraxylene to react for a period of time to obtain radial mesoporous SiO 2 A microsphere; in the step 1, the volume ratio of the alcohol to the water is 0.5-0.8:1; volume ratio of ammonia water to alcohol: 0.01-0.02:1, a step of; the volume ratio of the silicon source to the alcohol is 0.06-0.1:1; the reaction time is 2-4 h; the stirring speed is 600-800 rpm; adding paraxylene after adding silicon source for 2-10 min; the volume ratio of the ammonia water to the paraxylene is 0.15-0.3:1; the mass percentage of ammonia in the ammonia water is 25-28%;
step 2, adding a carbon source into the reaction system, stirring, fully reacting, centrifuging, washing, freeze-drying, drying and calcining the obtained solution to obtain SiO with the inner core 2 Is a nano carbon sphere; added carbon source and SiO 2 The mass ratio of the microspheres is more than 2;
step 3, siO in the nano carbon spheres in the step 2 is treated 2 And etching to obtain the porous carbon spheres with special core shells.
2. The method for preparing the core-shell special-shaped porous carbon spheres according to claim 1, wherein the method comprises the following steps: in the step 1, the surfactant is one of Cetyl Trimethyl Ammonium Bromide (CTAB) or Cetyl Trimethyl Ammonium Chloride (CTAC).
3. The method for preparing the core-shell special-shaped porous carbon spheres according to claim 1, wherein the method comprises the following steps: in the step 1, the silicon source is one or more of tetraethyl silicate, tetrapropyl silicate and silicon tetrachloride.
4. The method for preparing the core-shell special-shaped porous carbon spheres according to claim 1, wherein the method comprises the following steps: in the step 1, the alcohol is one or more of ethanol, methanol, n-propanol, isopropanol, ethylene glycol, benzyl alcohol, butanol, amyl alcohol, hexanol, octanol and 2-methyl-1-propanol.
5. The method for preparing the core-shell special-shaped porous carbon spheres according to claim 1, wherein the method comprises the following steps: in the step 2, the reaction time of the system is 1-48 h.
6. The method for preparing the core-shell special-shaped porous carbon spheres according to claim 1, wherein the method comprises the following steps: in the step 2, the carbon source is one of dopamine hydrochloride or phenolic resin.
7. The core-shell shaped porous carbon sphere prepared by the method according to any one of claims 1 to 6, wherein: the porous carbon sphere is characterized in that the inner core of the porous carbon sphere is a radial mesoporous carbon sphere, the outer shell is a hollow microsphere, the inner core of the porous carbon sphere is tightly connected with the outer shell, and the mesoporous aperture of the inner core and the shell thickness of the outer shell can be controlled and regulated; the particle size of the porous carbon sphere is 400-500 nm, and the thickness of the outer shell layer is more than 20nm.
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