CN109694071B - Method for preparing nitrogen-doped porous carbon material by taking coconut shell as raw material and application - Google Patents

Method for preparing nitrogen-doped porous carbon material by taking coconut shell as raw material and application Download PDF

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CN109694071B
CN109694071B CN201910067581.3A CN201910067581A CN109694071B CN 109694071 B CN109694071 B CN 109694071B CN 201910067581 A CN201910067581 A CN 201910067581A CN 109694071 B CN109694071 B CN 109694071B
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porous carbon
nitrogen
carbon material
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CN109694071A (en
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徐朗
张文都
王会芬
齐佳伟
白沛瑶
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China University of Mining and Technology CUMT
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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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a method for preparing a nitrogen-doped porous carbon material by taking coconut shells as raw materials and application thereof. The invention takes agricultural and forestry waste coconut shells with abundant resources and low cost as raw materials, and the prepared nitrogen-doped porous carbon material has large specific surface area and a multi-level pore structure, wherein the macropores are favorable for mass transmission, and the micropores and the mesopores can provide more active sites and improve the catalytic activity; the carbon material has strong resistance to methanol solution, good cycle stability and potential application prospect in oxygen reduction catalysts.

Description

Method for preparing nitrogen-doped porous carbon material by taking coconut shell as raw material and application
Technical Field
The invention belongs to the field of inorganic nano materials and electrochemistry, relates to a nitrogen-doped porous carbon material, and particularly relates to a method for preparing the nitrogen-doped porous carbon material by taking coconut shells as raw materials and application.
Background
The oxygen reduction reaction is an important process in novel energy conversion devices such as fuel cells, metal zinc air cells and the like, and the oxygen reduction reaction needs a catalyst with excellent performance because the dynamic process is slow and side reactions are more. For a long time, the oxygen reduction reaction in the actual device is catalyzed by noble metal catalysts such as platinum, palladium, iridium, etc., and the noble metal catalysts are expensive in cost, poor in durability, and easily poisoned by substances such as carbon monoxide and methanol, etc., thereby limiting the commercial development of new energy devices such as fuel cells. Therefore, the development of low-cost and high-performance non-noble metal catalysts capable of replacing the traditional noble metal catalysts has become an urgent task for the development of electrochemical energy conversion devices such as fuel cells and metal air.
Porous carbon materials have a rich pore structure, a high specific surface area, and good electrical conductivity, and have become popular catalyst materials. The introduction of the hetero element into the porous carbon material can increase the defects and active sites on the surface of the material, and further improve the surface structure of the material. The nitrogen atom is closest to the carbon atom due to the atomic size and electronegativity of the nitrogen atom, so that electrons can be provided for the carbon atom, the conductivity of the carbon material is improved, the charge transfer in the oxygen reduction process is promoted, the overpotential in the oxygen reduction process is reduced, and the electrocatalytic performance of the oxygen reduction is improved.
At present, the synthesis method of the nitrogen-doped porous carbon material mainly comprises two methods, one method is in-situ synthesis of a nitrogen-containing material, and the other method is high-temperature ammoniation treatment of the porous carbon after synthesis. CN103922305A discloses a preparation method of high-specific-surface-area high-nitrogen-content doped porous carbon, which comprises the steps of taking biomass coconut shells as raw materials, carrying out high-temperature carbonization treatment to obtain carbides, then dispersing the carbides in a potassium hydroxide saturated solution, and drying to obtain an alkali-carbon mixture; carrying out high-temperature activation treatment on the alkali-carbon mixture to obtain a porous carbon material; uniformly dispersing a porous carbon material in strong acid solution concentrated sulfuric acid for oxidation treatment, filtering, washing and drying to obtain an oxidized porous carbon material, and finally performing high-temperature ammoniation treatment on the oxidized porous carbon material in an ammonia atmosphere to obtain doped porous carbon. Although the doped porous carbon material with high specific surface area and high nitrogen content is obtained by the method, concentrated sulfuric acid strong acid solution is needed, the environment is not friendly, and the safety is low due to ammonia injection at high temperature.
Therefore, there is an urgent need to develop a method for synthesizing nitrogen-doped porous carbon materials with cleanness, environmental protection, low cost, high efficiency and safety.
Disclosure of Invention
The invention aims to provide a method for preparing a nitrogen-doped porous carbon material by taking coconut shells as raw materials, which is simple, environment-friendly and low in cost.
The invention also aims to provide the application of the nitrogen-doped porous carbon material prepared by taking the coconut shell as the raw material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for preparing a nitrogen-doped porous carbon material by taking coconut shells as raw materials comprises the following steps:
(1) crushing coconut shell, sieving to obtain shredded coconut, cleaning, drying, placing in a tube furnace, and keeping at 5 deg.C for min under protection of inert gas-1Heating to 400 ℃ at the speed of (1), keeping the temperature for 2h, and cooling to room temperature to obtain a pre-carbonized material A;
(2) washing the material A with potassium hydroxide solution at 60 ℃ for 8h, filtering, and washing with water until the filtrate is neutral; then acid washing with dilute hydrochloric acid solution for 1h at the temperature of 60 ℃, filtering, washing with water until the filtrate is neutral, and drying to obtain a material B;
(3) according to the mass ratio of 1: 3, respectively weighing potassium hydroxide and potassium bicarbonate to prepare a mixed solution, dispersing the material B in the mixed solution, stirring for 1h at the temperature of 60 ℃, then adding a melamine solution, continuously stirring for 2h, then transferring to a culture dish, and putting into a freeze dryer for freeze drying to obtain a material C;
(4) placing the material C in a tube furnace under the protection of inert gas at 2 deg.C for min-1The temperature is raised to 800 ℃ at the rate of (1) and kept for 2h, and then the temperature is raised for 5 min-1Cooling to 400 ℃ at the speed, and naturally cooling to room temperature to obtain a material D;
(5) and (3) pickling the material D with a dilute hydrochloric acid solution for 1 hour, filtering, washing with water until the filtrate is neutral, and drying to obtain the nitrogen-doped porous carbon material.
Preferably, in the step (3), the mass ratio of the material B to the potassium hydroxide in the mixed solution is 1: 1, the mass ratio of melamine to material B in the melamine solution is 4: 1.
preferably, in the step (2), the concentration of the potassium hydroxide solution is 6mol L-1。
Preferably, in the step (2) and the step (5), the concentration of the dilute hydrochloric acid solution is 1mol L-1。
Preferably, in the step (3), the stirring speed is 300r min-1。
Preferably, in the step (1) and the step (4), the inert gas is nitrogen or argon.
Preferably, in the step (5), the drying temperature is 80 ℃ and the drying time is 12 h.
The invention also provides application of the nitrogen-doped porous carbon material prepared by the preparation method in an oxygen reduction catalyst.
Uniformly mixing a nitrogen-doped porous carbon material with deionized water, isopropanol and a 5% perfluorosulfonic acid-polytetrafluoroethylene copolymer (Nafion) solution, carrying out ultrasonic treatment for 1h, dripping 8 mu l of the mixed solution on a Rotating Disk Electrode (RDE) with the diameter of 5mm, and naturally airing in the air to prepare the working electrode.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the nitrogen-doped porous carbon material is prepared by taking the natural biomass coconut shell with rich resources and low cost as a raw material, so that the effective reutilization of agricultural and forestry wastes is realized;
(2) the nitrogen-doped porous carbon material prepared by the invention has large specific surface area reaching 2126m2g-1And has a hierarchical pore structure with a total pore volume of 1.084cm3g-1The macropores are beneficial to mass transmission, and the micropores and the mesopores can provide more active sites and improve the catalytic activity; x-ray photoelectron spectroscopy (XPS) analysis indicates that the nitrogen content is 5%;
(3) the preparation method of the nitrogen-doped porous carbon material provided by the invention is simple and environment-friendly, and the oxygen reduction electrocatalysis performance is excellent and is equivalent to that of a commercial oxygen reduction Pt/C catalyst;
(4) the nitrogen-doped porous carbon material prepared by the invention has strong resistance to methanol solution, good circulation stability and potential application prospect in oxygen reduction catalysts.
Drawings
FIG. 1 shows that the nitrogen-doped porous carbon material prepared in example 1 of the present invention is saturated with nitrogen and oxygen by 0.1mol L-1Cyclic Voltammetry (CV) curves in potassium hydroxide solution;
FIG. 2 shows that the nitrogen-doped porous carbon material prepared in example 1 of the present invention is saturated with oxygen at 0.1mol L-1400-2025r min in potassium hydroxide solution-1Swept Voltammetry (LSV) curve of (a);
FIG. 3 shows the oxygen saturation of 0.1mol L of the nitrogen-doped porous carbon materials prepared in example 1 and comparative examples 1 to 4 of the present invention-11600r min in potassium hydroxide solution-1Swept Voltammetry (LSV) curve of (a);
FIG. 4 is an isothermal (77K) nitrogen adsorption and desorption curve of the nitrogen-doped porous carbon material prepared in example 1 of the present invention;
FIG. 5 is a graph of pore distribution calculated using a Discrete Fourier Transform (DFT) model for a nitrogen-doped porous carbon material prepared in example 1 of the present invention;
FIG. 6 is a Scanning Electron Microscope (SEM) electron micrograph of a nitrogen-doped porous carbon material prepared in example 1 of the present invention;
FIG. 7 shows a sample of nitrogen-doped porous carbon material obtained in example 1 of the present invention and Pt/C at 0.1mol L-1400r min at 0.7V in potassium hydroxide solution-1A methanol resistance map of (a);
FIG. 8 shows a sample of nitrogen-doped porous carbon material prepared in example 1 of the present invention and Pt/C at 0.1mol L-1400r min at 0.7V in potassium hydroxide solution-1Cycling stability plot of (1).
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
(1) Crushing coconut shell, sieving to obtain filamentous coconut shreds, washing with deionized water, drying, placing into corundum boat, and placing in a tube furnace at 5 deg.C for min in nitrogen atmosphere-1Heating to 400 ℃ at the speed of 2 hours, and naturally cooling to room temperature after heating to obtain a pre-carbonized material A1;
(2) the material A1 was transferred to a beaker and 100ml of 6mol L were added at 60 ℃-1Potassium hydroxide solution, 300r min-1Stirring for 8h, suction filtering, washing with deionized water until the filtrate is neutral, transferring the filter cake into a beaker, and adding 100ml of 1mol L at 60 DEG C-1HCI，300r min-1Stirring for 1h, performing suction filtration, washing with deionized water until the filtrate is neutral, and drying to obtain a material B1;
(3) dissolving 0.15g of potassium hydroxide and 0.45g of potassium bicarbonate in waterPreparing 20ml of mixed solution in ionized water, adding 0.15g of material B1 into the mixed solution, and heating at 60 deg.C for 300r min-1Stirring for 1h, adding 20ml of newly prepared solution dissolved with 0.6g of melamine, continuously stirring for 2h, pouring into a culture dish, putting into a freeze dryer, and freeze-drying for 24h to obtain a material C1;
(4) transferring the material C1 to a corundum boat, placing the corundum boat in a tube furnace, and carrying out nitrogen protection at 2 ℃ for min-1Raising the temperature to 800 ℃ at a speed rate for 2h, and then raising the temperature for 5 min-1Cooling to 400 ℃ at a speed, and naturally cooling to room temperature to obtain a material D1;
(5) the material D1 was transferred to a beaker and 100ml of 1mol L were added-1Stirring the HCI for 1h, carrying out suction filtration, washing the mixture to be neutral by using deionized water, and drying the mixture for 12h at the temperature of 80 ℃ to obtain the nitrogen-doped porous carbon material E1.
Weighing 3mg of nitrogen-doped porous carbon material E1, uniformly mixing the nitrogen-doped porous carbon material E1 with 170 mu l of deionized water, 70 mu l of isopropanol and 10 mu l of 5% perfluorosulfonic acid-polytetrafluoroethylene copolymer (Nafion) solution, carrying out ultrasonic treatment for 1h, dropping 8 mu l of mixed solution on a Rotating Disk Electrode (RDE) with the diameter of 5mm, and naturally airing in the air to prepare a working electrode; the electrode is taken as a working electrode, a platinum wire is taken as a counter electrode, a silver/silver chloride electrode with the thickness of 3.5m is taken as a reference electrode to form a three-electrode system, and the oxygen saturation is carried out at 0.1mol L-1The sweep rate of the cyclic voltammetry curve and the linear voltammetry curve in the potassium hydroxide solution is respectively 5mv s-1And 10mv s-1。
FIG. 1 shows 0.1mol L of the catalyst in example 1 saturated with nitrogen and oxygen-1Cyclic Voltammetry (CV) curves in potassium hydroxide solution at 0.1mol L saturated with oxygen-1The potassium hydroxide solution of example 1 has a distinct oxygen reduction peak, but does not exist in nitrogen, indicating that example 1 has good catalytic performance for oxygen reduction reaction.
FIG. 2 shows example 1 at 0.1mol L of oxygen saturation-1400-2025r min in potassium hydroxide solution-1It can be seen that the initial potential during the oxygen reduction reaction of example 1 is very positive, indicating that the overpotential of the reaction is low, and in addition, the curve has a distinct limiting current plateau and a limiting currentAnd has a large density, further illustrating that the example 1 has good catalytic performance for oxygen reduction reaction.
FIG. 4 shows the isothermal (77K) nitrogen desorption curve of example 1, which is tested to have a specific surface area of 2126m2g-1Total pore volume of 1.084cm3g-1Meanwhile, it can be seen from the figure that the material has a large adsorption capacity when the relative pressure is relatively small and a hysteresis loop when the relative pressure is greater than 0.5, which indicates that the material has rich micropores and a certain mesoporous and macroporous structure, and verifies that the example 1 has a hierarchical pore structure.
FIG. 5 is a graph of pore distribution calculated by Discrete Fourier Transform (DFT) model in example 1, showing that the material has abundant micropores at about 1nm and mesopores of 2-10nm, and also has a certain macropore at 50nm, and this result corresponds to FIG. 4.
Fig. 6 is a field emission Scanning Electron Microscope (SEM) photograph of example 1, and it can be seen that the material of example 1 has a distinct hierarchical pore structure, corresponding to fig. 4 and 5.
XPS analysis shows that the material prepared by the invention mainly contains C, N, O element, the nitrogen content is 5 percent, and further proves that nitrogen atoms are successfully doped into the material.
Comparative example 1
(1) Crushing coconut shell, sieving to obtain filamentous coconut shreds, washing with deionized water, drying, placing into corundum boat, and placing in a tube furnace at 5 deg.C for min in nitrogen atmosphere-1Heating to 400 ℃ at the speed of 2 hours, and naturally cooling to room temperature after heating to obtain a pre-carbonized material A2;
(2) the material A2 was transferred to a beaker and 100ml of 6mol L were added at 60 ℃-1Potassium hydroxide, 300rmin-1Stirring for 8h, then performing suction filtration, washing with deionized water until the filtrate is neutral, transferring the filter cake into a beaker, and adding 100ml of 1mol L at the temperature of 60 DEG C-1HCI，300r min-1Stirring for 1h, washing with deionized water to be neutral, and drying to obtain a material B2;
(3) transferring the material B2 to a corundum boat, placing the corundum boat in a tube furnace, and carrying out nitrogen protection at 2 ℃ for min-1Raising the temperature to 800 ℃ at a speed rate and keeping the temperature2h, then 5 ℃ min-1Cooling to 400 ℃ at a speed, and naturally cooling to room temperature to obtain the nitrogen-doped porous carbon material E2;
the electrochemical test method of the nitrogen-doped porous carbon material E2 as the oxygen reduction catalyst is the same as that of the embodiment 1.
Comparative example 2
(1) Crushing coconut shell, sieving to obtain filamentous coconut shreds, washing with deionized water, drying, placing into corundum boat, and placing in a tube furnace at 5 deg.C for min in nitrogen atmosphere-1Heating to 400 ℃ at the speed of 2 hours, and naturally cooling to room temperature after heating to obtain a pre-carbonized material A3;
(2) taking 0.15g of the material A3, 0.15g of potassium hydroxide, 0.45g of potassium bicarbonate and 0.6g of melamine at the rotating speed of 300rmin-1Carrying out vacuum ball milling for 30min under the condition to obtain a material B3;
(3) transferring the material B3 to a corundum boat, placing the corundum boat in a tube furnace, and carrying out nitrogen protection at 2 ℃ for min-1Raising the temperature to 800 ℃ at a speed rate for 2h, and then raising the temperature for 5 min-1Cooling to 400 ℃ at a speed, and naturally cooling to room temperature to obtain a material C3;
(4) the batch C3 was transferred into a beaker and 100ml of 1mol L were added-1Stirring the HCI for 1h, carrying out suction filtration, washing the mixture to be neutral by using deionized water, and drying the mixture for 12h at the temperature of 80 ℃ to obtain the nitrogen-doped porous carbon material E3.
The electrochemical test method of the nitrogen-doped porous carbon material E2 as the oxygen reduction catalyst is the same as that of the embodiment 1.
Comparative example 3
(1) Crushing coconut shell, sieving to obtain filamentous coconut shreds, washing with deionized water, drying, placing into corundum boat, and placing in a tube furnace at 5 deg.C for min in nitrogen atmosphere-1Heating to 400 ℃ at the speed of 2 hours, and naturally cooling to room temperature after heating to obtain a pre-carbonized material A4;
(2) dissolving 0.15g potassium hydroxide and 0.45g potassium bicarbonate in deionized water to obtain 20ml mixed solution, adding 0.15g material A4 into the mixed solution, and heating at 60 deg.C for 300r min-1Stirring for 1h, adding 20ml of newly prepared solution containing 0.6g of melamine, stirring for 2h, and pouring into a culture dishFreeze-drying in a freeze-drying machine for 24h to obtain a material B4;
(3) transferring the material B4 to a corundum boat, placing the corundum boat in a tube furnace, and carrying out nitrogen protection at 2 ℃ for min-1Raising the temperature to 800 ℃ at a speed rate for 2h, and then raising the temperature for 5 min-1Cooling to 400 ℃ at a speed, and naturally cooling to room temperature to obtain a material C4;
(4) the batch C4 was transferred into a beaker and 100ml of 1mol L were added-1Stirring the HCI for 1h, carrying out suction filtration, washing the mixture to be neutral by using deionized water, and drying the mixture for 12h at the temperature of 80 ℃ to obtain the nitrogen-doped porous carbon material E4.
The electrochemical test method of the nitrogen-doped porous carbon material E4 as the oxygen reduction catalyst is the same as that of the embodiment 1.
Comparative example 4
Weighing 1mg of commercial 20% Pt/C by using an electronic balance, uniformly mixing the Pt/C with 170 mu l of deionized water, 70 mu l of isopropanol and 10 mu l of 5% perfluorosulfonic acid-polytetrafluoroethylene copolymer (Nafion) solution, carrying out ultrasonic treatment for 1h, dripping 8 mu l of the mixed solution on a Rotating Disk Electrode (RDE) with the diameter of 5mm, and naturally airing in the air to prepare a working electrode; the electrode was used as a working electrode, a platinum wire was used as a counter electrode, and 3.5mol L of the electrode was used-1The silver/silver chloride electrode is a reference electrode to form a three-electrode system, and the oxygen saturation is 0.1mol L-1The sweep rate of the cyclic voltammetry curve and the linear voltammetry curve in the potassium hydroxide solution is respectively 5mv s-1s and 10mv s-1。
FIG. 3 shows the results of 0.1mol L of saturated oxygen in example 1 and comparative examples 1 to 4-11600r min in potassium hydroxide solution-1According to the sweep voltammetry (LSV) curve, the initial potential, half-wave potential and limiting current density of example 1 are obviously superior to those of comparative examples 1-3 and are equivalent to those of commercial Pt/C in comparative example 4, which shows that example 1 has excellent catalytic performance for oxygen reduction reaction which is comparable to that of the commercial Pt/C, and has good application prospect.
FIG. 7 shows the current at 0.1mol L by chronoamperometry-1Constant voltage (0.7V vsRhHE) 400 rpm in oxygen saturated potassium hydroxide solution-1The current for the oxygen reduction reaction was tested under conditions and 2.5ml of methanol solution (99%) was added at the 100 th s of the test. Such asAs shown in the graph, the commercial Pt/C catalyst of comparative example 4 has severe current fluctuation after methanol addition, while the material of example 1 has very little current fluctuation after methanol addition, which indicates that the material of example 1 has very good resistance to methanol.
FIG. 8 is a graph showing the measurement of 0.1mol L by the chronoamperometry-1Constant voltage (0.7V vsRhHE) 400 rpm in oxygen saturated potassium hydroxide solution-1The current of the oxygen reduction reaction was tested under the conditions. As shown, the current of the comparative example 4 commercial Pt/C catalyst decayed to less than 60% after 50000s testing, while the current of the example 1 material remained above 90%, indicating that the example 1 material had good stability and resistance.

Claims (7)

1. A method for preparing a nitrogen-doped porous carbon material by taking coconut shells as raw materials is characterized by comprising the following steps:
(1) crushing coconut shell, sieving to obtain shredded coconut, cleaning, drying, placing in a tube furnace, and keeping at 5 deg.C for min under protection of inert gas-1Heating to 400 ℃ at the speed of (1), keeping the temperature for 2h, and cooling to room temperature to obtain a pre-carbonized material A;
(2) washing the material A with potassium hydroxide solution at 60 ℃ for 8h, filtering, and washing with water until the filtrate is neutral; then acid washing with dilute hydrochloric acid solution for 1h at the temperature of 60 ℃, filtering, washing with water until the filtrate is neutral, and drying to obtain a material B;
(3) according to the mass ratio of 1: 3, respectively weighing potassium hydroxide and potassium bicarbonate to prepare a mixed solution, dispersing the material B in the mixed solution, stirring for 1h at the temperature of 60 ℃, then adding a melamine solution, continuously stirring for 2h, then transferring to a culture dish, and putting into a freeze dryer for freeze drying to obtain a material C; the mass ratio of the material B to the potassium hydroxide in the mixed solution is 1: 1, the mass ratio of melamine to material B in the melamine solution is 4: 1;
(4) placing the material C in a tube furnace under the protection of inert gas at 2 deg.C for min-1The temperature is raised to 800 ℃ at the rate of (1) and kept for 2h, and then the temperature is raised for 5 min-1Cooling to 400 ℃ at the speed, and naturally cooling to room temperature to obtain a material D;
(5) and (3) pickling the material D with a dilute hydrochloric acid solution for 1 hour, filtering, washing with water until the filtrate is neutral, and drying to obtain the nitrogen-doped porous carbon material.
2. The method for preparing nitrogen-doped porous carbon material from coconut shells as claimed in claim 1, wherein in the step (2), the concentration of the potassium hydroxide solution is 6mol L-1。
3. The method for preparing nitrogen-doped porous carbon material from coconut shells as claimed in claim 1, wherein the dilute hydrochloric acid solution has a concentration of 1mol L in step (2) and step (5)-1。
4. The method for preparing nitrogen-doped porous carbon material from coconut shell as claimed in claim 1, wherein in step (3), the stirring rate is 300r min-1。
5. The method for preparing nitrogen-doped porous carbon material from coconut shells as claimed in claim 1, wherein in step (1) and step (4), the inert gas is nitrogen or argon.
6. The method for preparing nitrogen-doped porous carbon material from coconut shells as claimed in claim 1, wherein in step (5), the drying temperature is 80 ℃ and the drying time is 12 h.
7. Use of a nitrogen-doped porous carbon material prepared by the method of any one of claims 1 to 6 in an oxygen reduction catalyst.
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CN112467109A (en) * 2020-11-27 2021-03-09 西安建筑科技大学 Activated carbon material, composite material, cathode material and cathode sheet of zinc ion energy storage device and zinc ion energy storage device
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