CN107161979B - Carbon-based nanobelt porous material, and preparation method and application thereof - Google Patents

Carbon-based nanobelt porous material, and preparation method and application thereof Download PDF

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CN107161979B
CN107161979B CN201710267452.XA CN201710267452A CN107161979B CN 107161979 B CN107161979 B CN 107161979B CN 201710267452 A CN201710267452 A CN 201710267452A CN 107161979 B CN107161979 B CN 107161979B
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nanobelt
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porous material
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nitrogen
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CN107161979A (en
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隋竹银
李欣
韩宝航
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National Center for Nanosccience and Technology China
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Abstract

The invention relates to a carbon-based nanobelt porous material, and a preparation method and application thereof, wherein hetero atoms are doped in the porous material, and the specific surface area is 500-1500 m2A pore volume of 0.5 to 2.5 cm/g3The pore diameter is 0.2 nm-10 mu m. The porous material has the characteristics of high specific surface area, excellent conductivity and the like, so that the porous material has good application in the fields of electrocatalysis, gas adsorption, supercapacitors, lithium ion batteries and the like. The invention also discloses a method for preparing the porous material, which comprises the following steps: carrying out polymerization reaction on a polymer monomer in the presence of a surfactant to generate a polymer nanobelt; and (3) placing the mixture at the temperature of 600-1000 ℃ to perform an activation reaction with an activating agent to obtain the catalyst. The method is simple and convenient to operate, low in cost and suitable for large-scale production.

Description

Carbon-based nanobelt porous material, and preparation method and application thereof
Technical Field
The invention relates to a carbon material, a preparation method and application thereof, in particular to a nanobelt porous material, and a preparation method and application thereof.
Background
In the twenty-first century, the development of green sustainable energy conversion and storage technologies has become important due to the consumption of fossil fuels and the environmental problems associated with the use of fossil fuels. The oxygen reduction reaction is a key step in electrochemical energy conversion and storage systems such as metal air batteries and fuel cells. Platinum is known to be the best catalyst, but the problems of high cost, poor stability and methanol tolerance inhibit the development of platinum on the commercial road. Therefore, researchers have been working on developing electrocatalysts that are inexpensive, stable, and have excellent performance.
Porous materials have been a focus of research in materials science. Over the past few decades, a variety of porous materials, such as porous carbon, metal organic frameworks, covalent organic frameworks, porous silica, and zeolites have made significant progress. Porous carbon materials have attracted much attention as potential electrocatalysts due to their excellent electrical conductivity, high specific surface area, good chemical stability and low cost. However, the electrocatalytic performance of most porous carbon materials still needs to be improved.
Heteroatom doping is a common technique for modifying materials. The introduction of the heteroatom plays an important role in changing the chemical property of the porous carbon material and improving the electrocatalytic activity of the porous carbon material. In recent years, materials such as nano wires, nano fibers, nano tubes or nano ribbons with nano structures have been widely researched by researchers, and they have been widely applied to the fields of catalysis, gas storage, supercapacitors, batteries, sensors, and the like. The carbon-based nanobelt is a one-dimensional carbon-based nanomaterial, and reports on the carbon-based nanobelt are rare at present. A nitrogen doped carbon based nanoribbon porous material was prepared by potassium hydroxide activation of polypyrrole nanoribbons by young et al (ind. eng. chem. res.2016,55, 6384-. However, the activating agent used in this method is very corrosive to the equipment and requires post-treatment of the activated material.
Disclosure of Invention
Based on the above technical background, the present invention aims to provide a carbon-based nanoribbon porous material, wherein the porous material uses carbon-based nanoribbons as units, and is one-dimensionally connected to form a network structure;
the specific surface area of the porous material is 500-1500 m2(ii)/g; the pore volume is 0.5-2.5 cm3(ii)/g; the aperture is 0.2 nm-10 mu m; the carbon-based nanobelt porous material is doped with heteroatoms;
preferably, the specific surface area is 850-1280 m2A pore volume of 0.8 to 1.5 cm/g3(ii)/g; the aperture is 0.5 nm-1 μm.
More preferably, the heteroatom is nitrogen or sulfur, and may also contain both nitrogen and sulfur.
The carbon-based nanobelt porous material has the characteristics of large specific surface area, wide aperture and the like.
Hetero atoms doped in the carbon-based nanobelt porous material can change the chemical properties of the carbon-based nanobelt porous material, and can specifically improve the performances of electrocatalysis, gas adsorption, supercapacitors and lithium ion batteries.
The nitrogen atom or the sulfur atom has larger electronegativity than the carbon atom, so that the electron cloud distribution on the chemical bond is uneven, the interaction between the carbon-based porous material and gas or ions is favorably enhanced, and the performances of electro-catalysis, gas adsorption, a super capacitor and a lithium ion battery are improved. The introduction of nitrogen atoms or sulfur atoms can also lead to the increase of defect sites of the carbon-based porous material, and can also be beneficial to enhancing the interaction between the carbon-based porous material and gas or ions, thereby improving the performance.
A second object of the present invention is to provide a method for preparing the aforementioned carbon-based nanobelt porous material, wherein the method comprises the steps of:
1) carrying out polymerization reaction on the polymer monomer under the action of a surfactant to generate a polymer nanobelt;
2) and (3) placing the polymer nanobelt at the temperature of 600-1000 ℃, and carrying out an activation reaction with an activating agent to obtain the carbon-based nanobelt porous material.
The mass ratio of the polymer monomer to the surfactant is 0.5-2: 1;
the polymer monomer is selected from one or more of pyrrole, aniline and 3, 4-ethylenedioxythiophene;
the surfactant is hexadecyl trimethyl ammonium bromide;
the activating agent is one or more of carbon dioxide, water vapor and oxygen;
wherein the use of different polymer monomers affects the formation of different heteroatoms. For example, pyrrole and aniline are used as polymer monomers, so that a nitrogen heteroatom-doped carbon-based nanobelt porous material can be prepared; and 3, 4-ethylenedioxythiophene is taken as a polymer monomer, so that the carbon-based nanobelt porous material doped with sulfur heteroatoms can be prepared. Therefore, in actual production, the polymer monomer is specifically selected according to the application range of the porous material.
The surfactant mainly used in the current experimental process is cetyl trimethyl ammonium bromide, and other types of surfactants can hardly achieve the expected effect.
The method is simple to operate, and the polymer nanobelt is subjected to activation reaction with one or more of carbon dioxide, water vapor and oxygen at high temperature, so that the heteroatom-doped carbon-based nanobelt porous material can be obtained in one step.
Further provides a preparation method of the carbon-based nanobelt porous material, wherein the polymerization reaction specifically comprises the following steps: mixing the polymer monomer solution with the surfactant solution, fully mixing, adding a catalyst, and carrying out polymerization reaction for 10-30 hours at the temperature of 1-5 ℃;
preferably, the post-polymerization treatment comprises catalyst removal, drying;
more preferably, the temperature of the polymerization reaction is 4 ℃; the time of the polymerization reaction is 24 hours;
further preferably, the catalyst is selected from one or more of ammonium persulfate and potassium persulfate.
Different types of polymers correspond to different monomers, some reactions require a catalyst, and some reactions can occur without a catalyst. The use of the catalyst can promote the reaction and also can greatly improve the reaction efficiency and reduce the reaction time. In practice, the choice of catalyst is not fixed and depends on the different monomers of the polymer and on the polymerization conditions. For example, the polymerization of pyrrole or thiophene can be catalyzed by ammonium persulfate or potassium persulfate, in which case the polymerization is a free radical polymerization mechanism.
Preferably, taking pyrrole monomer as an example, the preparation method of the polypyrrole nanobelt comprises the following steps:
1) dissolving cetyl trimethyl ammonium bromide in water, adding pyrrole monomer, fully mixing until the mixture is clear, and adding ammonium persulfate solution to obtain mixed solution;
2) placing the mixed solution obtained in the step 1) at a temperature of 1-5 ℃ for a polymerization reaction for 10-30 h to obtain a mixture;
3) carrying out suction filtration on the mixture obtained in the step 2), and washing by using water and an organic solvent; and drying the polypyrrole nano-belt to obtain the polypyrrole nano-belt.
The mass ratio of the hexadecyl trimethyl ammonium bromide to the pyrrole monomer is 0.8-1.5: 1;
the amount of the hexadecyl trimethyl ammonium bromide added in the step 1) is that 1-6mmol of hexadecyl trimethyl ammonium bromide is added into each 100-1000 mL of ultrapure water; wherein 100-800 mu L of pyrrole monomer and 1-6mmol of ammonium persulfate can be mixed;
the mixing in the step 1) adopts ultrasonic mixing, wherein the power of the ultrasonic is 10-600W, and the frequency of the ultrasonic is 20-200 KHz;
the step 1) of mixing also comprises stirring, wherein the stirring time is 1-30 min; the ammonium persulfate solution is added in a dropwise manner; pre-cooling the ammonium persulfate solution before dripping;
while stirring, placing the mixed solution in an ice bath condition, and dropwise adding an ammonium persulfate solution while stirring;
the polymerization reaction can be carried out in a refrigerator, the temperature of the refrigerator is set to a target temperature in advance, and the mixed liquid is put into the refrigerator after the temperature is constant.
Step 2) the organic solvent is acetone; the using amount of the acetone is 100-1000 mL;
the temperature of the drying treatment is 60-100 ℃;
the drying treatment is carried out in an oven.
Taking pyrrole monomers as an example, the preparation method of the polypyrrole nanobelt comprises the following steps:
1) dissolving 1-6mmol of hexadecyl trimethyl ammonium bromide in 100-1000 mL of ultrapure water, and ultrasonically dissolving; adding 100-800 mu L of pyrrole monomer, ultrasonically dissolving, and mixing until the mixture is clear; stirring for 1-5 min, stirring for a general formula, and dropwise adding a solution with the volume of 30-100mL and the amount of ammonium persulfate of 1-6mmol to obtain a mixed solution;
2) placing the mixed solution obtained in the step 1) at a temperature of 1-5 ℃ for a polymerization reaction for 10-30 h to obtain a mixture;
3) carrying out suction filtration on the mixture obtained in the step 2), and washing by using 100-1000 mL of ultrapure water and 100-1000 mL of acetone; and drying at 60-100 deg.C to obtain polypyrrole nanometer belt.
Further provides a preparation method of the carbon-based nanobelt porous material, wherein the activation reaction time in the step 2) is 1-10 hours; the preheating rate of the activation reaction is 2-50 ℃/min; the cooling rate after the activation reaction is 2-50 ℃/min; the temperature of the activation reaction is 750-950 ℃;
preferably, the time of the activation reaction is 1 to hours; the preheating rate of the activation reaction is 2-10 ℃/min; the cooling rate after the activation reaction is 2-10 ℃/min;
more preferably, the time of the activation reaction is 2 to hours: the preheating rate of the activation reaction is 5-10 ℃/min; and the cooling rate after the activation reaction is 5-10 ℃/min.
The activation reaction is carried out in inert gas or nitrogen at a pre-heating temperature;
preferably, the inert gas is argon;
in the process of activation reaction, the earlier heating atmosphere is inert gas or nitrogen, when the temperature is raised to the target temperature, the inert gas or nitrogen is discharged, and one or more of carbon dioxide, water vapor and oxygen are injected to complete the activation reaction;
cooling to room temperature after the activation reaction, wherein the room temperature is generally between 15 and 25 ℃, and the room temperature can also float in a small range; this temperature difference has little effect on the formation of the porous material;
the activation reaction is carried out in a tube furnace; preferably, the activation reaction is carried out in a high temperature tube furnace.
The preparation method of the carbon-based nanobelt porous material provided by the invention can adopt the following steps:
1) adding a polymer monomer solution into hexadecyl trimethyl ammonium bromide, fully mixing, adding ammonium persulfate, and carrying out polymerization reaction for 10-30 hours at 1-5 ℃; removing ammonium sulfate, and drying at 60-100 ℃ to obtain a polymer nanobelt;
the polymer monomer is selected from pyrrole, aniline and 3, 4-ethylenedioxythiophene;
2) placing the polymer nanobelt in argon or nitrogen, and heating to 750-950 ℃ at the speed of 5-10 ℃/min; removing argon or nitrogen, injecting one or more of carbon dioxide, water vapor and oxygen, and carrying out activation reaction for 2-6 hours; and cooling to room temperature at the speed of 5-10 ℃/min to obtain the carbon-based nanobelt porous material.
As a preferred scheme, taking pyrrole monomer as an example, the preparation method of the carbon-based nanobelt porous material provided by the invention can adopt the following steps:
1) adding pyrrole monomer solution into hexadecyl trimethyl ammonium bromide, fully mixing, adding ammonium persulfate, and placing at 4 ℃ for polymerization reaction for 24 hours; removing ammonium sulfate, and drying at 60-100 deg.C to obtain polypyrrole nanobelt;
2) putting the polypyrrole nanobelt in argon or nitrogen, and heating to 750-950 ℃ at the speed of 5-10 ℃/min; removing argon or nitrogen, injecting carbon dioxide or water vapor, and carrying out activation reaction for 2-6 hours; and cooling to room temperature at the speed of 5-10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt porous material.
The inventor makes a plurality of experiments to find that when the carbon-based nanobelt porous material is prepared, the reaction temperature, the reaction time, the activated gas, the heating rate and the cooling rate in the activation process all influence the specific surface area, the pore volume and the pore size distribution of the porous material; in particular, the temperature and time of the activation reaction and the effect of the activated gas are greatly affected.
The third purpose of the invention is to apply the prepared carbon-based nanobelt porous material to electrocatalysis, gas adsorption, supercapacitors and lithium ion batteries;
when the carbon-based nanobelt porous material is used as an electrocatalyst of an oxygen reduction reaction, the electron transfer number is 3.5-4.1, and the initial potential is 0.75-0.92V.
The preparation method of the carbon-based nanobelt porous material is simple and convenient to operate, low in cost and suitable for large-scale production.
The carbon-based nanobelt porous material has the advantages of high specific surface area, large pore volume, three-dimensional network porous structure, excellent oxygen reduction reaction performance and good circulation stability, and shows excellent performance in the field of electrocatalysis.
In addition, the carbon-based nanobelt porous material can also be widely applied to the fields of supercapacitors, gas adsorption and separation, lithium ion batteries and the like.
Drawings
Fig. 1 is a scanning electron micrograph of a nitrogen-doped carbon-based nanoribbon porous material prepared in example 3, and an inset in fig. 1 is a transmission electron micrograph of the nitrogen-doped carbon-based nanoribbon porous material prepared in example 3;
fig. 2 is a nitrogen adsorption and desorption graph of the nitrogen-doped carbon-based nanobelt porous material prepared in example 3;
fig. 3 is an X-ray diffractometer spectrum of the nitrogen-doped carbon-based nanobelt porous material prepared in example 3;
fig. 4 is an X-ray photoelectron spectrum of the nitrogen-doped carbon-based nanobelt porous material prepared in example 3;
fig. 5 is a cyclic voltammogram of the nitrogen-doped carbon-based nanobelt porous material prepared in example 3 in an aqueous potassium hydroxide solution containing saturated oxygen or saturated nitrogen;
fig. 6 is a graph of the time response of the nitrogen doped carbon-based nanoribbon porous material prepared in example 3 and a commercial platinum/carbon material in an aqueous potassium hydroxide solution containing saturated oxygen;
fig. 7 is a time-series response curve of the nitrogen-doped carbon-based nanobelt porous material prepared in example 3 and a commercial platinum/carbon material before and after adding methanol to an aqueous potassium hydroxide solution containing saturated oxygen.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Wherein, the following examples take pyrrole monomers as examples to prepare polypyrrole nanobelts; the polypyrrole nano-band is prepared by the following method:
1) dissolving 3mmol of hexadecyl trimethyl ammonium bromide in 300mL of ultrapure water, and ultrasonically dissolving until the solution is clear; adding 300 mu L of pyrrole monomer into the mixture, and carrying out ultrasonic dissolution until the mixture is clear; the power of the ultrasonic wave is 200W, and the frequency of the ultrasonic wave is 40 KHz;
2) stirring the mixed solution obtained in the step 1) for about 5min under an ice bath condition, keeping vigorous stirring, and dropwise adding pre-cooled 65mL of ammonium persulfate solution into the mixed solution, wherein the 65mL of persulfate solution contains 4.5mmol of ammonium persulfate;
3) placing the mixture obtained in the step 2) in a refrigerator at 4 ℃ for polymerization reaction for 24 hours; and (3) carrying out suction filtration on the reacted mixture, respectively washing the mixture by using 500mL of ultrapure water and 500mL of acetone, and drying the mixture in an oven at 80 ℃ to obtain the polypyrrole nanobelt.
Example 1
Placing the obtained polypyrrole nanobelt in a quartz boat, and transferring the quartz boat into a tube furnace; the tube furnace temperature was raised to 750 ℃ in a nitrogen atmosphere at a ramp rate of 10 ℃/min. When the temperature of the tube furnace reaches 750 ℃, nitrogen is discharged, carbon dioxide is injected, and the tube furnace is activated for 2 hours in the carbon dioxide atmosphere. And then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt porous material.
Example 2
The obtained polypyrrole nanobelt was placed in a quartz boat, and then transferred to a tube furnace. The temperature of the tube furnace was increased to 850 ℃ in a nitrogen atmosphere at a heating rate of 10 ℃/min. When the temperature of the tubular furnace reaches 850 ℃, releasing nitrogen, injecting carbon dioxide, and activating for 2h in carbon dioxide atmosphere. And then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt material.
Example 3
The obtained polypyrrole nanobelt was placed in a quartz boat, and then transferred to a tube furnace. The tube furnace temperature was raised to 950 ℃ in a nitrogen atmosphere at a ramp rate of 10 ℃/min. When the temperature of the tube furnace reaches 950 ℃, nitrogen is discharged, carbon dioxide is injected, and the tube furnace is activated for 6 hours in the carbon dioxide atmosphere. And then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt material.
The nitrogen-doped carbon-based nanobelt porous material prepared in example 3 was subjected to the related experiments, and the results were as follows:
fig. 1 is a scanning electron microscope photograph of the nitrogen-doped carbon-based nanoribbon porous material prepared in example 3, and it can be seen from fig. 1 that the nanoribbons in the nitrogen-doped carbon-based nanoribbon porous material have a length of about several micrometers, and are cross-linked with each other to form a network structure. The inset in fig. 1 is a transmission electron micrograph of the nitrogen-doped carbon-based nanoribbon porous material prepared in example 3, and the one-dimensional nanoribbon structure of the nitrogen-doped carbon-based nanoribbon porous material can be seen from the inset in fig. 1.
FIG. 2 is a graph showing nitrogen adsorption and desorption curves of the nitrogen-doped carbon-based nanoribbon porous material prepared in example 3, and it can be seen from FIG. 2 that the prepared nitrogen-doped carbon-based nanoribbon porous materials each have a hierarchical porous structure with a specific surface area of 1130m2g–1。
Fig. 3 is an X-ray diffractometer spectrum of the nitrogen-doped carbon-based nanobelt porous material prepared in example 3, and it can be seen from fig. 3 that the prepared porous material shows a broad peak at about 24 ° (interlayer spacing of about 0.37 nm).
Fig. 4 is an X-ray photoelectron spectrum of the nitrogen-doped carbon-based nanoribbon porous material prepared in example 3, and it can be seen from fig. 4 that the prepared porous material contains three elements of nitrogen, oxygen and sulfur.
Fig. 5 is a cyclic voltammetry curve of the nitrogen-doped carbon-based nanoribbon porous material prepared in example 3 in a potassium hydroxide aqueous solution containing saturated oxygen or saturated nitrogen, and it can be seen from fig. 5 that the prepared nitrogen-doped carbon-based nanoribbon porous material has an obvious reduction peak in the potassium hydroxide aqueous solution containing saturated oxygen and shows better electrocatalytic activity.
Fig. 6 is a graph showing the time response of the nitrogen-doped carbon-based nanoribbon porous material prepared in example 3 and a commercial platinum/carbon material in an aqueous potassium hydroxide solution containing saturated oxygen, and it can be seen from fig. 6 that the nitrogen-doped carbon-based nanoribbon porous material has better stability than the commercial platinum/carbon material.
Fig. 7 is a time-series response curve of the nitrogen-doped carbon-based nanoribbon porous material prepared in example 3 and a commercial platinum/carbon material before and after adding methanol to an aqueous potassium hydroxide solution containing saturated oxygen, and it can be seen from fig. 7 that the nitrogen-doped carbon-based nanoribbon porous material has better methanol tolerance than the commercial platinum/carbon material.
Example 4
The obtained polypyrrole nanobelt was placed in a quartz boat, and then transferred to a tube furnace. The tube furnace temperature was raised to 950 ℃ in a nitrogen atmosphere at a ramp rate of 30 ℃/min. When the temperature of the tube furnace reaches 950 ℃, nitrogen is discharged, carbon dioxide is injected, and the tube furnace is activated for 6 hours in the carbon dioxide atmosphere. And then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt material.
Example 5
Placing the obtained polypyrrole nanobelt in a quartz boat, and transferring the quartz boat into a tube furnace; the tube furnace temperature was raised to 750 ℃ in a nitrogen atmosphere at a ramp rate of 10 ℃/min. When the temperature of the tube furnace reaches 750 ℃, nitrogen is discharged, water vapor is injected, and the tube furnace is activated for 2 hours in the water vapor atmosphere. And then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt porous material.
Example 6
Placing the obtained polypyrrole nanobelt in a quartz boat, and transferring the quartz boat into a tube furnace; the temperature of the tube furnace was increased to 850 ℃ in a nitrogen atmosphere at a heating rate of 10 ℃/min. When the temperature of the tubular furnace reaches 850 ℃, nitrogen is discharged, water vapor is injected, and the tubular furnace is activated for 2 hours in the water vapor atmosphere. And then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt porous material.
Example 7
Placing the obtained polypyrrole nanobelt in a quartz boat, and transferring the quartz boat into a tube furnace; the tube furnace temperature was raised to 950 ℃ in a nitrogen atmosphere at a ramp rate of 10 ℃/min. When the temperature of the tube furnace reaches 950 ℃, nitrogen is discharged, water vapor is injected, and the tube furnace is activated for 2 hours in the atmosphere of the water vapor. And then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt porous material.
Example 8
Placing the obtained polypyrrole nanobelt in a quartz boat, and transferring the quartz boat into a tube furnace; the temperature of the tube furnace was increased to 850 ℃ in a nitrogen atmosphere at a heating rate of 10 ℃/min. When the temperature of the tubular furnace reaches 850 ℃, nitrogen is discharged, water vapor is injected, and the tubular furnace is activated for 6 hours in the water vapor atmosphere. And then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt porous material.
Example 9
The obtained polypyrrole nanobelt was placed in a quartz boat, and then transferred to a tube furnace. The tube furnace temperature was raised to 950 ℃ in a nitrogen atmosphere at a rate of 5 ℃/min. When the temperature of the tube furnace reaches 950 ℃, nitrogen is discharged, carbon dioxide is injected, and the tube furnace is activated for 2 hours in the carbon dioxide atmosphere. And then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt material.
Example 10
Placing the obtained polypyrrole nanobelt in a quartz boat, and transferring the quartz boat into a tube furnace; the temperature of the tube furnace was increased to 850 ℃ in a nitrogen atmosphere at a rate of 5 ℃/min. When the temperature of the tubular furnace reaches 850 ℃, nitrogen is discharged, water vapor is injected, and the tubular furnace is activated for 2 hours in the water vapor atmosphere. And then cooling to room temperature at a cooling rate of 10 ℃/min to obtain the nitrogen-doped carbon-based nanobelt porous material.
Example 11
Placing the obtained polypyrrole nanobelt in a quartz boat, and transferring the quartz boat into a tube furnace; the temperature of the tube furnace was increased to 850 ℃ in a nitrogen atmosphere at a rate of 5 ℃/min. When the temperature of the tubular furnace reaches 850 ℃, nitrogen is discharged, water vapor is injected, and the tubular furnace is activated for 6 hours in the water vapor atmosphere. And then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the nitrogen-doped carbon-based nanobelt porous material.
Example 12
The obtained polypyrrole nanobelt was placed in a quartz boat, and then transferred to a tube furnace. The tube furnace temperature was raised to 950 ℃ in a nitrogen atmosphere at a rate of 5 ℃/min. When the temperature of the tube furnace reaches 950 ℃, nitrogen is discharged, carbon dioxide is injected, and the tube furnace is activated for 6 hours in the carbon dioxide atmosphere. And then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the nitrogen-doped carbon-based nanobelt material.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (14)

1. A carbon-based nanobelt porous material is characterized in that the porous material takes carbon-based nanobelts as units and is connected into a net structure in one dimension;
wherein hetero atoms are doped in the porous material; the specific surface area of the porous material is 850-1280 m2A pore volume of 0.8 to 1.5 cm/g3(ii)/g; the aperture is 0.5 nm-1 μm; the heteroatom is a nitrogen heteroatom or/and a sulfur heteroatom;
the method for preparing the carbon-based nanobelt porous material comprises the following steps of:
1) fully mixing a polymer monomer with a surfactant, adding a catalyst, and carrying out polymerization reaction for 10-30 hours at the temperature of 1-5 ℃ to generate a polymer nanobelt; the polymer monomer is selected from one or more of pyrrole, aniline and 3, 4-ethylenedioxythiophene; the surfactant is cetyl trimethyl ammonium bromide; the catalyst is selected from one or more of ammonium persulfate, potassium persulfate and sodium persulfate;
2) placing the polymer nanobelt at the temperature of 750-950 ℃, and carrying out an activation reaction with an activating agent to obtain a carbon-based nanobelt porous material; the activating agent is selected from one or more of carbon dioxide and water vapor;
the activation reaction time is 1-10 hours; the preheating rate of the activation reaction is 2-50 ℃/min; and the cooling rate after the activation reaction is 2-50 ℃/min.
2. A method of preparing the carbon-based nanoribbon porous material of claim 1, comprising the steps of:
1) fully mixing a polymer monomer with a surfactant, adding a catalyst, and carrying out polymerization reaction for 10-30 hours at the temperature of 1-5 ℃ to generate a polymer nanobelt; the polymer monomer is selected from one or more of pyrrole, aniline and 3, 4-ethylenedioxythiophene; the surfactant is cetyl trimethyl ammonium bromide; the catalyst is selected from one or more of ammonium persulfate, potassium persulfate and sodium persulfate;
2) placing the polymer nanobelt at the temperature of 750-950 ℃, and carrying out an activation reaction with an activating agent to obtain a carbon-based nanobelt porous material; the activating agent is selected from one or more of carbon dioxide and water vapor;
the activation reaction time is 1-10 hours; the preheating rate of the activation reaction is 2-50 ℃/min; and the cooling rate after the activation reaction is 2-50 ℃/min.
3. The method according to claim 2, wherein the mass ratio of the polymer monomer to the surfactant is 0.5-2: 1.
4. the process according to any one of claims 2 to 3, wherein the polymerization reaction of step 1) is in particular: mixing a polymer monomer and a surfactant by ultrasonic waves until the mixture is clear to obtain a mixed solution; and (3) dripping a pre-cooling catalyst into the mixed solution, and carrying out polymerization reaction for 24 hours at the temperature of 4 ℃.
5. The method according to any one of claims 2 to 3, wherein the activation reaction of step 2) is carried out at a pre-elevated temperature in an inert gas or nitrogen; when the target temperature is reached, the inert gas or the nitrogen is switched into an activating agent to carry out an activation reaction;
wherein the inert gas is selected from one or more of argon, helium, neon, krypton and xenon.
6. The method according to claim 4, wherein the activation reaction of step 2) is carried out at a pre-elevated temperature in an inert gas or nitrogen; when the target temperature is reached, the inert gas or the nitrogen is switched into an activating agent to carry out an activation reaction;
wherein the inert gas is selected from one or more of argon, helium, neon, krypton and xenon.
7. The method according to any one of claims 2, 3 and 6, wherein the activation reaction time is 1-6 hours; or the preheating rate of the activation reaction is 2-10 ℃/min; and the cooling rate after the activation reaction is 2-10 ℃/min.
8. The method according to claim 4, wherein the time of the activation reaction is 1 to 6 hours; or the preheating rate of the activation reaction is 2-10 ℃/min; and the cooling rate after the activation reaction is 2-10 ℃/min.
9. The method according to claim 5, wherein the time of the activation reaction is 1 to 6 hours; or the preheating rate of the activation reaction is 2-10 ℃/min; and the cooling rate after the activation reaction is 2-10 ℃/min.
10. The method according to claim 7, wherein the activation reaction time is 2-6 hours: the preheating rate of the activation reaction is 5-10 ℃/min; and the cooling rate after the activation reaction is 5-10 ℃/min.
11. The method according to claim 8 or 9, wherein the activation reaction is carried out for 2 to 6 hours: the preheating rate of the activation reaction is 5-10 ℃/min; and the cooling rate after the activation reaction is 5-10 ℃/min.
12. A method according to any one of claims 2-3, characterized in that the method comprises in particular the steps of:
1) adding a polymer monomer solution into cetyl trimethyl ammonium bromide, fully mixing, adding ammonium persulfate, placing at 4 ℃, carrying out polymerization reaction for 24 hours, and drying to obtain a polymer nanobelt;
2) placing the polymer nanobelt in argon or nitrogen, and heating to 750-950 ℃ at the speed of 5-10 ℃/min; removing argon or nitrogen, injecting carbon dioxide or water vapor, and carrying out activation reaction for 2-6 hours; and cooling to room temperature at the speed of 5-10 ℃/min to obtain the carbon-based nanobelt porous material.
13. The method according to claim 4, characterized in that it comprises in particular the steps of:
1) adding a polymer monomer solution into cetyl trimethyl ammonium bromide, fully mixing, adding ammonium persulfate, placing at 4 ℃, carrying out polymerization reaction for 24 hours, and drying to obtain a polymer nanobelt;
2) placing the polymer nanobelt in argon or nitrogen, and heating to 750-950 ℃ at the speed of 5-10 ℃/min; removing argon or nitrogen, injecting carbon dioxide or water vapor, and carrying out activation reaction for 2-6 hours; and cooling to room temperature at the speed of 5-10 ℃/min to obtain the carbon-based nanobelt porous material.
14. The use of the carbon-based nanoribbon porous material of claim 1 in electrocatalysis, gas adsorption, supercapacitors and lithium ion batteries.
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