CN110775956A - Sulfur-doped ordered mesoporous carbon nanosphere with straight pore channel structure, preparation method and application - Google Patents
Sulfur-doped ordered mesoporous carbon nanosphere with straight pore channel structure, preparation method and application Download PDFInfo
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Abstract
The invention discloses a sulfur-doped ordered mesoporous carbon nanosphere with a straight pore channel structure, a preparation method and application thereof. The sulfur-doped ordered mesoporous carbon nanospheres have the particle size of 100-300 nm, and the sulfur-doped ordered mesoporous carbon nanospheres have a body-centered cubic mesoporous structure, wherein the body-centered cubic mesoporous structure comprises a plurality of straight pore channels distributed on the surface of the sulfur-doped ordered mesoporous carbon nanospheres and penetrating through the sulfur-doped ordered mesoporous carbon nanospheres, and the pore diameter of each straight pore channel is 2-5 nm. The preparation method has the advantages of simple and controllable process, low cost, easy repetition, environmental protection and the like; meanwhile, the sulfur-doped ordered mesoporous carbon nanospheres with the straight pore channel structure synthesized by the method have the characteristics of unique pore channel morphology and large specific surface area, and the material has good performance in a lithium metal battery through tests and has wide application prospect in future lithium ion batteries.
Description
Technical Field
The invention belongs to the technical field of mesoporous material preparation, and particularly relates to a sulfur-doped ordered mesoporous carbon nanosphere with a straight pore channel structure, and a preparation method and application thereof.
Background
The ordered mesoporous carbon material has the characteristics of ordered structure, large specific surface area, uniform and adjustable pore diameter, good conductivity, good stability and the like, is a hotspot of current research, and can be widely applied to the fields of supercapacitors, fuel cells, lithium batteries, hydrophobic drug carriers and the like. These unique chemical and physical properties make them ideal candidates for high power density battery electrode materials. In addition, compared with widely used commercial graphite carbon, the ordered mesoporous carbon material has good interconnectivity among pores, is favorable for penetration and transportation of electrolyte ions, and has better electrochemical performance under high current density. Researches show that the mechanical property, the semiconductor property, the field emission property and the electrical property of the carbon material can be obviously enhanced by adding heteroatoms such as boron, nitrogen, oxygen, sulfur and the like into carbon lattices. In recent years, many works have been done in the preparation of element-doped mesoporous carbon nanoparticles, wherein sulfur doping can enhance the surface polarity, conductivity and electron donor tendency of mesoporous carbon, so that it has been widely applied in the fields of capacitors, fuel cells, catalysis, etc.
Disclosure of Invention
The invention mainly aims to provide a sulfur-doped ordered mesoporous carbon nanosphere with a straight pore channel structure, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a sulfur-doped ordered mesoporous carbon nanosphere with a straight pore channel structure, wherein the particle size of the sulfur-doped ordered mesoporous carbon nanosphere is 100-300 nm, the sulfur-doped ordered mesoporous carbon nanosphere has a body-centered cubic phase mesoporous structure, the body-centered cubic phase mesoporous structure comprises a plurality of straight pore channels distributed on the surface of the sulfur-doped ordered mesoporous carbon nanosphere and penetrating through the sulfur-doped ordered mesoporous carbon nanosphere, and the pore diameter of each straight pore channel is 2-5 nm.
The embodiment of the invention also provides a preparation method of the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure, which comprises the following steps:
reacting a uniformly mixed aqueous phase reaction system containing phenol, an aldehyde compound, a sulfur source and a surfactant to obtain a high-molecular prepolymer;
carrying out hydrothermal reaction on a hydrothermal reaction system containing the high-molecular prepolymer to obtain a solid matter;
and roasting the solid in a protective atmosphere to obtain the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure.
The embodiment of the invention also provides the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure prepared by the method.
The embodiment of the invention also provides application of the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure in preparation of super capacitors, fuel cells and lithium metal batteries.
The embodiment of the invention also provides a lithium metal battery which comprises the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a novel mesoporous carbon material, namely an ordered mesoporous carbon nanosphere with a straight pore passage, which opens up a new application field for ordered mesoporous carbon;
(2) compared with the traditional mesoporous carbon, the synthesis time of the novel mesoporous carbon material is greatly shortened, and the efficiency is effectively improved, so that the energy can be saved, and the novel mesoporous carbon material is green and environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an X-ray scattering diagram of sulfur-doped ordered mesoporous carbon nanospheres with a straight-channel structure prepared in example 1 of the present invention;
FIGS. 2a-2b are transmission electron micrographs of sulfur-doped ordered mesoporous carbon nanospheres with a straight pore structure prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a field emission microscope of sulfur-doped ordered mesoporous carbon nanospheres with a straight pore structure prepared in example 1 of the present invention;
fig. 4 is a test chart of a symmetric cell of the sulfur-doped ordered mesoporous carbon nanosphere with a straight pore channel structure prepared in example 1 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a large amount of practice, and the present invention is based on an organic-organic self-assembly strategy, selects a triblock copolymer F127 (polyethylene oxide-polypropylene oxide-polyethylene oxide) as a surfactant, takes phenol, a sulfur source and an aldehyde compound as high molecular monomers, adopts a hydrothermal combination in-situ one-step reduction technology, and realizes effective regulation and control of the pore structure and the morphology of an ordered mesoporous carbon material by changing the proportion or the concentration of the high molecular monomers and experimental process conditions, so as to obtain the ordered functional mesoporous material with a large specific surface area and a short straight pore channel, and the ordered functional mesoporous material is expected to be widely applied to the aspects of supercapacitors, fuel cells, lithium batteries, etc.
One aspect of the embodiments of the present invention provides a sulfur-doped ordered mesoporous carbon nanosphere with a straight pore channel structure, wherein the particle size of the sulfur-doped ordered mesoporous carbon nanosphere is 100nm to 300nm, the sulfur-doped ordered mesoporous carbon nanosphere has a body-centered cubic phase mesoporous structure, the body-centered cubic phase mesoporous structure comprises a plurality of straight pore channels distributed on the surface of the sulfur-doped ordered mesoporous carbon nanosphere and penetrating through the sulfur-doped ordered mesoporous carbon nanosphere, and the pore diameter of each straight pore channel is 2nm to 5 nm.
Further, the particle size of the sulfur-doped ordered mesoporous carbon nanospheres is 200-300 nm, and the pore diameter of the straight pore channel is 3-4 nm.
Furthermore, the nanospheres are synthesized by roasting phenolic resin at high temperature, and can be also called mesoporous carbon nanospheres.
Further, the hole is a straight hole.
In another aspect of the embodiments of the present invention, there is provided a method for preparing the sulfur-doped ordered mesoporous carbon nanosphere with a straight pore channel structure, which includes:
reacting a uniformly mixed aqueous phase reaction system containing phenol, an aldehyde compound, a sulfur source and a surfactant to obtain a high-molecular prepolymer;
carrying out hydrothermal reaction on a hydrothermal reaction system containing the high-molecular prepolymer to obtain a solid matter;
and roasting the solid in a protective atmosphere to obtain the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure.
In some more specific embodiments, the preparation method comprises:
uniformly mixing phenol, an aldehyde compound, a sulfur source, strong base and water, reacting for 0.5-1 h at 66-75 ℃, and then adding a surfactant to form a uniformly mixed aqueous phase reaction system;
and (3) reacting the uniformly mixed aqueous phase reaction system for 2-4 hours at 66-70 ℃, adding water for diluting by 20-30 times, and continuing to react for 16-20 hours at 66-70 ℃ to obtain the high-molecular prepolymer.
In some more specific embodiments, the preparation method may comprise:
(1) mixing phenol, a sulfur source, an excessive aldehyde compound and strong base in an aqueous phase system, reacting for 0.5-1 h at 66-75 ℃, adding a surfactant, continuing to react for 2-4 h at 66-70 ℃, adding water for diluting by 20-30 times, and continuing to react for 16-20 h to obtain a high-molecular prepolymer;
(2) adding the high-molecular prepolymer into water, carrying out hydrothermal treatment at 120-130 ℃ for more than 20-24 hours, and then filtering, washing and drying to obtain a solid, wherein the solid is light yellow solid powder;
(3) and roasting the solid at 700-1000 ℃ for 2-3 h in a protective atmosphere to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure.
In some more specific embodiments, the preparation method further comprises:
(1) dissolving phenol and a sulfur source in water to form a mixed solution, adding an excessive aldehyde compound and strong base, reacting at 66-75 ℃ for 0.5-1 h, adding a surfactant, continuously reacting at 66-70 ℃ and a stirring speed of 300-400 rpm for more than 2-4 h, adding water for dilution, and continuously reacting for more than 16-20 h to obtain a high-molecular prepolymer;
(2) adding the high-molecular prepolymer into water, carrying out hydrothermal treatment at 120-130 ℃ for more than 20-24 hours, and then filtering, washing and drying to obtain a solid, wherein the solid is light yellow solid powder;
(3) and roasting the solid at 700-1000 ℃ for 2-3 h in a protective atmosphere to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure.
Further, the aldehyde compound comprises any one of formaldehyde, acetaldehyde and propionaldehyde; formaldehyde is preferred.
In a preferred embodiment, the synthesis of the polymer prepolymer comprises:
A. dissolving phenol and a sulfur source in water at 40 ℃ to form a mixed solution;
B. adding formaldehyde and strong base into the mixed solution obtained in the step A, and continuously stirring at 70 ℃ for 0.5 h;
C. adding surfactant (for example, the preferable proportion can be 0.96g F127 dissolved in 15ml water, but is not limited to the preferred proportion), and stirring for more than 2h under the conditions that the temperature is 70 ℃ and the rotating speed is 350 rpm;
D. and D, adding water into the mixture obtained in the step C for dilution, and continuously stirring for more than 16 hours until red precipitates appear, so as to obtain the high-molecular phenolic resin prepolymer.
Further, the protective atmosphere includes a nitrogen atmosphere, an inert gas atmosphere, but is not limited thereto.
Furthermore, the molar ratio of the mixture of the phenol and the sulfur source to the aldehyde compound to the strong base is (3-5): (7-12): 1.
Further, the molar ratio of the phenol to the sulfur source is 1:3-3: 1.
Further, the sulfur source includes any one of p-hydroxyphenethiol, m-hydroxyphenethiol, and hydroxythiophene, without being limited thereto.
Further, the surfactant includes F127, but is not limited thereto, and the F127 is a triblock polymer (polyoxyethylene-polyoxypropylene-polyoxyethylene) having a molecular formula of PEO-PPO-PEO.
Further, the molar ratio of the surfactant to the mixture of phenol and sulfur source is (2-4): 150-350).
Further, the strong base includes any one of sodium hydroxide and potassium hydroxide, but is not limited thereto.
Further, the concentration of the aldehyde compound solution is 35-40 wt%.
The embodiment of the invention also provides the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure prepared by the method.
In another aspect of the embodiment of the present invention, the application of the sulfur-doped ordered mesoporous carbon nanospheres with the straight pore channel structure in the preparation of supercapacitors, fuel cells and lithium metal batteries is also provided.
In another aspect of the embodiments of the present invention, there is also provided a lithium metal battery, which includes the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
And (3) performance characterization:
the various intermediate and final products involved in the synthesis of this example (collectively referred to hereinafter as "samples") can be structurally characterized by the following means:
the transmission electron microscope is obtained under 200kV by a Japanese JEOL JEM2011 type high-resolution transmission electron microscope;
scanning electron micrographs were obtained on a cold field emission scanning electron microscope, model S4800, manufactured by HITACHI, Japan, at 3.0 kV;
fig. 1 is an X-ray scattering diagram of a sulfur-doped ordered mesoporous carbon nanosphere with a straight pore structure prepared in example 1 of the present invention, which can be seen to have a highly ordered body-centered cubic phase pore structure;
fig. 2a-2b are transmission electron microscope images of sulfur-doped ordered mesoporous carbon nanospheres with a straight pore structure prepared in example 1 of the present invention, which can observe the existence of mesoporous pores on the surface of the nanospheres, and are special short straight pores;
fig. 3 is a field emission scanning electron microscope image of the sulfur-doped ordered mesoporous carbon nanospheres with a straight-channel structure prepared in example 1 of the present invention, and it can be seen that the nanospheres are spherical particles with relatively uniform size and average diameter of about 200 nm. It can also be clearly seen from the combination of FIGS. 2a-2b and FIG. 3 that the nanospheres prepared in example 1 have a highly ordered body-centered cubic phase pore structure;
fig. 4 is a test chart of a symmetric cell with sulfur-doped ordered mesoporous carbon nanospheres with a straight pore structure prepared in example 1 of the present invention;
it was found by testing that the material prepared in example 1 was at 0.5mA.cm
-2，1mAh.cm
-2Can be stably cycled for 1600h, and has a smaller overpotential compared to the comparative example, the sulfur-doped ordered mesoporous carbon nanospheres (SMC-2) coated with the material having a straight pore channel structure prepared in example 1 of the present invention showed better performance in a lithium metal battery compared to Cu sheets not coated with the material.
Example 2
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and hydroxythiophene into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 30min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 3
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% acetaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 120min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 4
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 1.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 5
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 60 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 6
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 80 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 7
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 90 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 8
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.48g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 9
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 120min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 10
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 700 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 11
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 1000 ℃ under the protection of argon to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 12
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 2 hours at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure.
Example 13
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 4 hours at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure.
Example 14
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and M-hydroxythiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% propionaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring for 2h at the rotating speed of 350rpm, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 18ml of high polymer prepolymer into a 100ml hydrothermal kettle, adding 56ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 15
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 120 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 16
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 140 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 4 hours at 1000 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 17
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 20 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 18
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 120 ℃ for 28 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 19
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at the rotating speed of 250rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 20
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.1M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 450rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 21
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.05M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
Example 22
(1) Synthesizing a high-molecular prepolymer: adding a certain amount of phenol and p-hydroxyphenylthiophenol into a three-neck flask at 40 ℃, adding 2.1ml of 35-40 wt% formaldehyde solution, heating to 70 ℃, continuing to stir for 30min, adding 15ml of 0.20M sodium hydroxide solution, continuing to stir for 60min, adding 15ml of aqueous solution dissolved with 0.96g of surfactant F127, adjusting the temperature to 66 ℃, stirring at 350rpm for 2h, adding 50ml of water for dilution, continuing to stir for 16-18h until red precipitates appear, stopping heating, cooling to room temperature, and preparing a high-molecular prepolymer after the generated precipitates are dissolved;
(2) putting the prepared 36ml of high polymer prepolymer into a 250ml hydrothermal kettle, adding 112ml of water for dilution, reacting the hydrothermal kettle in an oven at 130 ℃ for 24 hours, cooling to room temperature, centrifuging the solid aged in the hydrothermal kettle, washing with distilled water, and drying to obtain light yellow solid powder;
(3) and roasting the prepared light yellow solid powder for 3h at 800 ℃ under the protection of argon gas to obtain a target product, namely the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore structure.
The ordered mesoporous carbon nanosphere is a novel mesoporous material, has the characteristics of unique pore morphology, larger specific surface area, different-phase mesoporous structures and the like, and has the advantages of simple and controllable preparation process, low cost, easiness in repetition, environmental friendliness and the like. The invention opens up a new synthesis technology and application field for the sulfur-doped ordered mesoporous carbon.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. The sulfur-doped ordered mesoporous carbon nanospheres with the straight pore channel structure are characterized in that: the sulfur-doped ordered mesoporous carbon nanospheres have the particle size of 100-300 nm, and the sulfur-doped ordered mesoporous carbon nanospheres have a body-centered cubic mesoporous structure, wherein the body-centered cubic mesoporous structure comprises a plurality of straight pore channels distributed on the surface of the sulfur-doped ordered mesoporous carbon nanospheres and penetrating through the sulfur-doped ordered mesoporous carbon nanospheres, and the pore diameter of each straight pore channel is 2-5 nm.
2. A preparation method of sulfur-doped ordered mesoporous carbon nanospheres with a straight pore channel structure is characterized by comprising the following steps of:
reacting a uniformly mixed aqueous phase reaction system containing phenol, an aldehyde compound, a sulfur source and a surfactant to obtain a high-molecular prepolymer;
carrying out hydrothermal reaction on a hydrothermal reaction system containing the high-molecular prepolymer to obtain a solid matter;
and roasting the solid in a protective atmosphere to obtain the sulfur-doped ordered mesoporous carbon nanosphere with the straight pore channel structure.
3. The production method according to claim 2, characterized by comprising:
uniformly mixing phenol, an aldehyde compound, a sulfur source, strong base and water, reacting for 0.5-1 h at 66-75 ℃, and then adding a surfactant to form a uniformly mixed aqueous phase reaction system;
and (3) reacting the uniformly mixed aqueous phase reaction system for 2-4 hours at 66-70 ℃, adding water for diluting by 20-30 times, and continuing to react for 16-20 hours at 66-70 ℃ to obtain the high-molecular prepolymer.
4. The production method according to claim 3, characterized by comprising:
dissolving phenol and a sulfur source in water to form a mixed solution, adding an aldehyde compound and strong base, reacting at 66-75 ℃ for 0.5-1 h, and then adding a surfactant to form the uniformly mixed aqueous phase reaction system;
or adding phenol and a sulfur source into the aldehyde compound solution, continuously stirring for 0.5-1 h at 66-75 ℃, then adding strong base, continuously stirring for 0.5-1 h at 70-75 ℃, and then adding a surfactant to form the uniformly mixed aqueous phase reaction system;
preferably, the stirring speed is maintained at 300 to 400rpm during the reaction.
5. The method of claim 2, further comprising: and after the hydrothermal reaction is finished, filtering, washing and drying the obtained reaction system to obtain the solid matter.
6. The method of claim 2, wherein: the temperature of the hydrothermal reaction is 120-130 ℃, and the time is 20-24 h;
and/or the roasting treatment temperature is 700-1000 ℃, and the time is 2-3 h;
and/or the sulfur source comprises any one of p-hydroxyphenethiol, m-hydroxyphenethiol and hydroxythiophene;
and/or the aldehyde compound comprises any one of formaldehyde, acetaldehyde and propionaldehyde; preferably, the aldehyde compound is formaldehyde;
and/or the protective atmosphere comprises a nitrogen atmosphere and/or an inert gas atmosphere.
7. The method according to claim 3 or 4, wherein the molar ratio of the mixture of phenol and sulfur source, the aldehyde compound, and the strong base is (3-5): (7-12): 1; preferably, the molar ratio of phenol to sulfur source is 1:3 to 3: 1;
and/or, the surfactant comprises polyethylene oxide-polypropylene oxide-polyethylene oxide; preferably, the molar ratio of the surfactant to the mixture of phenol and sulfur source is (2-4): 150-350);
and/or, the strong base comprises sodium hydroxide and/or potassium hydroxide;
and/or the concentration of the aldehyde compound solution is 35 wt% -45 wt%.
8. Sulfur-doped ordered mesoporous carbon nanospheres with a straight pore channel structure prepared by the method of any of claims 2-7.
9. Use of the sulfur-doped ordered mesoporous carbon nanospheres with a straight pore channel structure as claimed in claim 1 in the preparation of supercapacitors, fuel cells, lithium metal batteries.
10. A lithium metal battery comprising the sulfur-doped ordered mesoporous carbon nanoball having a straight pore channel structure of claim 1 or 8.
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