CN113321200B - Preparation method of nitrogen-doped or iron-nitrogen-codoped hierarchical porous carbon spheres and application of carbon spheres in electrocatalytic oxygen reduction reaction - Google Patents
Preparation method of nitrogen-doped or iron-nitrogen-codoped hierarchical porous carbon spheres and application of carbon spheres in electrocatalytic oxygen reduction reaction Download PDFInfo
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Abstract
The invention discloses a preparation method of nitrogen-doped or iron-nitrogen-codoped hierarchical porous carbon spheres and application of the carbon spheres in electrocatalytic oxygen reduction reaction. According to the invention, a limited-domain polymerization strategy is adopted, formaldehyde is used as a carbon source, prepolymerization is carried out under the induction of the structures and the shapes of a nitrogen source precursor, a silicon source precursor and a surfactant, and then hydrothermal further polymerization is carried out; the reaction system is in a near-neutral condition, no strong acid or strong base catalyst is required to be additionally added, corrosion and loss of reaction equipment are reduced, and large-scale production is facilitated. The iron-nitrogen co-doped hierarchical pore carbon sphere material prepared by the method has a complete spherical structure, a large specific surface area and rich pore structures, is beneficial to exposure of active sites, has excellent oxygen reduction electrocatalysis performance, is expected to replace platinum-based catalysts in the technical field of electrocatalysis energy, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of carbon material catalysts, and particularly relates to a preparation method of nitrogen-doped or iron-nitrogen-doped hierarchical porous carbon spheres and application of the nitrogen-doped or iron-nitrogen-doped hierarchical porous carbon spheres in electrocatalytic oxygen reduction reaction.
Background
With the shortage of fossil energy and the increasing problem of environmental pollution, the demand for environment-friendly renewable energy is increasing. Fuel cells and metal-air cells have the advantages of high energy density, high conversion efficiency, little environmental pollution and the like, and are widely researched by people. However, the cathode oxygen reduction kinetics of fuel cells and metal-air cells are slow, limiting their development. At present, the catalyst for Oxygen Reduction Reaction (ORR) in the cathode is mainly platinum-based noble metal material, but the wide commercial application of the catalyst is limited due to the factors of high price, instability, easy agglomeration, easy poisoning and the like.
The hierarchical porous carbon material is an ideal catalytic host for anchoring an active object through physical and chemical interactions due to its porosity, large specific surface area, interpenetrating pore structure, high conductivity and stability, and plays a very important role in many practical application fields. However, the fabrication of hierarchical porous carbon microspheres with fine-structured, inter-crosslinked through-structures is more challenging than the fabrication of conventional carbon nanospheres because it is relatively difficult to achieve the fine control required for internal structure and external morphology from micro-scale to nano-scale. In order to further improve the catalytic performance of the heteroatom-doped porous carbon, the structure-activity relationship of the porous carbon is studied to show that the spherical material with the high specific surface area and the hierarchical pore structure is beneficial to the exposure of active sites and provides a rapid mass transfer process, so that the active sites are allowed to be accessed more easily, and the catalytic performance of the catalyst is improved.
Disclosure of Invention
Based on the background, the invention aims to provide a preparation method of a nitrogen-doped or iron-nitrogen-doped hierarchical porous carbon sphere and application thereof in electrocatalytic oxygen reduction reaction, wherein the nitrogen-doped or iron-nitrogen-doped hierarchical porous carbon sphere has oxygen reduction electrocatalytic performance equivalent to that of a platinum-carbon material under an alkaline condition.
The preparation method of the nitrogen-doped hierarchical pore carbon sphere comprises the following steps:
1) dissolving a nitrogen source precursor and a surfactant in water, then adding a silicon source precursor and ethanol, and uniformly stirring at 10-40 ℃; adding 35-40wt% of formaldehyde water solution to initiate polymerization, and continuously reacting for 1-15h at 10-40 ℃ to obtain milk white prepolymer; then transferring the mixture into a high-pressure reaction kettle, carrying out hydrothermal reaction for 12-24h at the temperature of 90-120 ℃, standing, washing, centrifuging, drying and grinding to obtain light yellow powder;
2) carbonizing the light yellow powder obtained in the step 1) at high temperature under the nitrogen condition, wherein the heating rate is 3-5 ℃/min, calcining for 1-3h when the temperature is raised to 350-;
3) adding the carbonized product obtained in the step 2) into a hydrofluoric acid solution, stirring for 3-12h at room temperature, filtering, and drying the washed product to obtain the nitrogen-doped hierarchical pore carbon sphere.
The first preparation method of the iron-nitrogen co-doped hierarchical pore carbon sphere comprises the following steps:
1) dissolving a nitrogen source precursor, a surfactant and an iron source precursor in water, then adding a silicon source precursor and ethanol, and uniformly stirring at 10-40 ℃; adding 35-40wt% of formaldehyde water solution to initiate polymerization, and continuously reacting for 1-15h at 10-40 ℃ to obtain milk white prepolymer; then transferring the mixture into a high-pressure reaction kettle, carrying out hydrothermal reaction for 12-24h at the temperature of 90-120 ℃, standing, washing, centrifuging, drying and grinding to obtain light yellow powder;
2) carbonizing the light yellow powder obtained in the step 1) at high temperature under the nitrogen condition, wherein the heating rate is 3-5 ℃/min, calcining for 1-3h when the temperature is raised to 350-;
3) adding the carbonized product obtained in the step 2) into a hydrofluoric acid solution, stirring for 3-12h at room temperature, filtering, and drying the washed product at 60-90 ℃ to obtain the iron-nitrogen co-doped hierarchical porous carbon sphere.
The second preparation method of the iron-nitrogen co-doped hierarchical pore carbon sphere comprises the following steps:
1) dissolving a nitrogen source precursor and a surfactant in water, then adding a silicon source precursor and ethanol, and uniformly stirring at 10-40 ℃; adding 35-40wt% of formaldehyde water solution to initiate polymerization, and continuously reacting for 1-15h at 10-40 ℃ to obtain milk white prepolymer;
2) adding an iron source precursor into the prepolymer obtained in the step 1), and stirring for reaction for 1-8 h; then transferring the mixture into a high-pressure reaction kettle, carrying out hydrothermal reaction for 12-24h at 90-120 ℃, standing, washing, centrifuging, drying at 60-90 ℃, and grinding to obtain light yellow powder;
3) carbonizing the light yellow powder obtained in the step 2) at high temperature under the nitrogen condition, wherein the heating rate is 3-5 ℃/min, calcining for 1-3h when the temperature is raised to 350-;
4) adding the carbonized product obtained in the step 3) into a hydrofluoric acid solution, stirring for 3-12h at room temperature, filtering, and drying the washed product at 60-90 ℃ to obtain the iron-nitrogen co-doped hierarchical porous carbon sphere.
The nitrogen source precursor is selected from one or more of 2, 6-diaminopyridine, 2-aminopyridine and 2-amino-6-methylpyridine.
The surfactant is selected from one or more of nonionic surfactants F127, F108 and P123.
The silicon source precursor is selected from one or more of silane reagents TEOS, TMOS and BTEB.
The iron source precursor is selected from one or more of ferric acetylacetonate, iron phthalocyanine and iron acetate.
The mass ratio of the nitrogen source precursor to the surfactant is 3: 0.8-4.
The mass ratio of the surfactant to the silicon source precursor is 0.1-2: 2.325.
The mass ratio of the ethanol to the surfactant is 1.76-8.78: 1.
The mass ratio of the surfactant to the water is 0.2-1: 100.
The mass ratio of the nitrogen source precursor to the formaldehyde is 0.5-1.6: 1.625.
The addition amount of the iron source precursor is not more than 16% of the mass of the nitrogen source precursor.
The prepared nitrogen-doped or iron-nitrogen-codoped hierarchical porous carbon spheres are applied to electrocatalytic oxygen reduction reaction. The specific conditions of the electrocatalytic oxygen reduction reaction are as follows: mixing nitrogen-doped or iron-nitrogen-codoped hierarchical porous carbon spheres with ethanol and Nafion solution, performing ultrasonic dispersion, then dropwise coating on a glassy carbon electrode, drying to obtain a working electrode, introducing oxygen into saturated alkaline electrolyte, and performing electrocatalytic oxygen reduction reaction by using a three-electrode system, wherein the platinum electrode is a counter electrode, and Ag/AgCl is a reference electrode.
According to the invention, a limited-domain polymerization strategy is adopted, formaldehyde is used as a carbon source, prepolymerization is carried out under the structural and morphological induction of a nitrogen source precursor, a silicon source precursor and a surfactant, and then hydrothermal further polymerization is carried out; the reaction system is in a near-neutral condition, no strong acid or strong base catalyst is required to be additionally added, corrosion and loss of reaction equipment are reduced, and large-scale production is facilitated. The iron-nitrogen co-doped hierarchical pore carbon sphere material prepared by the method has a complete spherical structure, a large specific surface area and rich pore structures, is beneficial to exposure of active sites, has excellent oxygen reduction electrocatalysis performance, is expected to replace platinum-based catalysts in the technical field of electrocatalysis energy, and has a good application prospect.
Drawings
FIG. 1 is a TEM image of N/C-900 of the nitrogen-doped multi-level pore carbon sphere obtained in example 1.
FIG. 2 is a TEM image of Fe-N/C-0 of the Fe-N co-doped hierarchical porous carbon sphere obtained in example 2.
FIG. 3 is a TEM image of Fe-N/C of the Fe-N co-doped hierarchical porous carbon sphere obtained in example 3.
FIG. 4 is a nitrogen absorption diagram and a pore size distribution diagram of Fe-N/C iron-nitrogen co-doped hierarchical porous carbon spheres obtained in example 3.
FIG. 5 is a graph of oxygen reduction electrocatalytic LSV tests performed in example 3. a. b is respectively an oxygen reduction LSV graph obtained by testing the iron-nitrogen co-doped hierarchical porous carbon sphere Fe-N/C at different rotating speeds and an oxygen reduction LSV comparison graph with a Pt/C material at 1600 rpm.
FIG. 6 is a graph showing methanol tolerance and stability tests performed in example 3.
The specific implementation mode is as follows:
example 1
Preparing nitrogen-doped hierarchical porous carbon spheres:
0.75g of 2, 6-diaminopyridine and 0.45g of F127 are dissolved in 33mL of deionized water, stirred at 30 ℃ until the solution is clear, and then 2.325g of TEOS and 3.95g of ethanol are added and stirred uniformly. 1.5mL of an aqueous formaldehyde solution (37 wt%) was added dropwise with slow stirring, and the reaction was continued for 12 hours with stirring at 30 ℃ to obtain a milky prepolymer. Transferring the mixture into a reaction kettle for further polymerization at 100 ℃ for 24h in a hydrothermal mode. And then washing the product with deionized water and ethanol, drying for one night at 60 ℃, and fully grinding to obtain light yellow powder. Carbonizing a sample at high temperature under nitrogen at the heating rate of 5 ℃/min, calcining for 1h when the temperature is raised to 350 ℃, continuously heating to 900 ℃ for carbonizing for 2h, and naturally cooling to room temperature under the nitrogen atmosphere to obtain a black carbonized product. And etching and carbonizing the product for 12 hours by using 10 wt% of HF, filtering, washing by using deionized water and ethanol, and drying at 60 ℃ to obtain the N/C-900 nitrogen-doped hierarchical pore carbon sphere.
As can be seen from the TEM photograph of FIG. 1, the N/C-900 material of the nitrogen-doped hierarchical porous carbon sphere has a monodisperse hollow spherical morphology, a complete spherical structure, a diameter of about 200-300nm, and a rich porous structure, which is beneficial to the exposure of active sites and is beneficial to the improvement of the electrocatalysis performance of oxygen reduction.
Oxygen reduction electrocatalytic test:
5mg of the prepared nitrogen-doped hierarchical pore carbon sphere N/C-900 is taken as a catalyst, 960 mu L of absolute ethyl alcohol and 40 mu L of 0.5 wt% Nafion solution are added into the catalyst, and the material is uniformly dispersed in the solution by ultrasonic treatment for 30 min. A glassy carbon electrode (diameter 5mm) was polished with 0.5 μm, 50nm alumina polishing powder in this order to obtain a smooth mirror surface. And dripping 20 mu L of the prepared catalyst uniform dispersion liquid on the surface of the polished glassy carbon electrode twice, and drying at room temperature. And performing electrochemical test in an electrochemical workstation (CHI760E), adopting a three-electrode system, and taking a platinum electrode, an Ag/AgCl reference electrode and a rotating disc electrode containing a glassy carbon electrode as a counter electrode, a reference electrode and a working electrode respectively, firstly introducing nitrogen into a saturated 0.1MKOH electrolyte for testing, and then introducing oxygen into the saturated 0.1MKOH electrolyte for testing.
Example 2:
preparing an iron-nitrogen co-doped hierarchical pore carbon sphere:
0.75g of 2, 6-diaminopyridine, 0.45g of F127 and 0.12g of iron acetylacetonate are dissolved in 33mL of deionized water and stirred at 30 ℃ until the solution is clear, and then 2.325g of TEOS and 3.95g of ethanol are added and stirred uniformly. 1.5mL of formaldehyde solution (37 wt%) was added dropwise with slow stirring, and the reaction was continued for 12 hours with stirring at 30 ℃ to give a milky white prepolymer. Transferring the mixture into a reaction kettle for further polymerization at 100 ℃ for 24h in a hydrothermal mode. And then washing the product with deionized water and ethanol, drying for one night at 60 ℃, and fully grinding to obtain light yellow powder. Carbonizing a sample at high temperature under nitrogen at the heating rate of 5 ℃/min, calcining for 1h when the temperature is raised to 350 ℃, continuously heating to 900 ℃ for carbonizing for 2h, and naturally cooling to room temperature under the nitrogen atmosphere to obtain a black carbonized product. And etching the carbonized product by using 10 wt% of HF for 12 hours, filtering, washing by using deionized water and ethanol, and drying at 60 ℃ to obtain the Fe-N co-doped hierarchical porous carbon sphere Fe-N/C-0.
As can be seen from the TEM photograph of FIG. 2, the Fe-N co-doped hierarchical porous carbon sphere Fe-N/C-0 material has a monodisperse spherical morphology and a rich porous structure, and the diameter is between about 100 and 160 nm.
The oxygen reduction electrocatalytic test procedure was the same as in example 1.
Example 3:
preparing an iron-nitrogen co-doped hierarchical pore carbon sphere:
0.75g of 2, 6-diaminopyridine and 0.45g of F127 are dissolved in 33mL of deionized water, stirred at 30 ℃ until the solution is clear, and then 2.325g of TEOS and 3.95g of ethanol are added and stirred uniformly. 1.5mL of an aqueous formaldehyde solution (37 wt%) was added dropwise with slow stirring, and the reaction was continued for 12h with stirring at 30 ℃. Then, 0.12g of iron acetylacetonate was added to the above solution and reacted with stirring at 30 ℃ for 1 hour to obtain a prepolymer. Transferring the mixture into a reaction kettle for further polymerization at 100 ℃ for 24h in a hydrothermal mode. And then washing the product with deionized water and ethanol, drying for one night at 60 ℃, and fully grinding to obtain light yellow powder. Carbonizing a sample at high temperature under nitrogen at the heating rate of 5 ℃/min, calcining for 1h when the temperature is raised to 350 ℃, continuously heating to 900 ℃ for carbonizing for 2h, and naturally cooling to room temperature under the nitrogen atmosphere to obtain a black carbonized product. And etching the carbonized product by using 10 wt% of HF for 12 hours, filtering, washing by using deionized water and ethanol, and drying at 60 ℃ to obtain the Fe-N co-doped hierarchical porous carbon sphere Fe-N/C.
As can be seen from the TEM photograph of FIG. 3, the Fe-N co-doped hierarchical porous carbon sphere Fe-N/C material has a monodisperse spherical morphology, has a diameter of about 200-300nm, has a rich porous structure, is beneficial to the exposure of active sites, and is beneficial to the improvement of the electrocatalysis performance of oxygen reduction. As shown in fig. 4, the Fe-N/C material has a hierarchical pore structure of micropores and mesopores.
The oxygen reduction electrocatalytic test procedure was the same as in example 1. The material prepared in the example 3 has higher oxygen reduction electrocatalytic performance compared with the materials prepared in the examples 1 and 2, and meanwhile, the half-wave potential of the material is 0.88V (vs. RHE) which is better than that of the Pt/C catalyst by 0.84V (vs. RHE), which shows that the material has excellent oxygen reduction electrocatalytic performance.
As can be seen from fig. 6, the material prepared in example 3 has better methanol resistance and stability than the commercial Pt/C catalyst. In the methanol resistance test, the limiting current hardly changed after adding 3M methanol at 300 s. Meanwhile, in a stability test, the limiting current retention rate reaches 98.5% after 20000s, and is better than 82.8% of that of a Pt/C catalyst.
Claims (8)
1. The preparation method of the nitrogen-doped hierarchical pore carbon sphere is characterized by comprising the following specific steps:
1) dissolving a nitrogen source precursor and a surfactant in water, then adding a silicon source precursor and ethanol, and uniformly stirring at 10-40 ℃; adding 35-40wt% of formaldehyde aqueous solution to initiate polymerization, and continuously reacting for 1-15h at 10-40 ℃ to obtain milk white prepolymer; then transferring the mixture into a high-pressure reaction kettle, carrying out hydrothermal reaction for 12-24h at the temperature of 90-120 ℃, standing, washing, centrifuging, drying and grinding to obtain light yellow powder;
2) carbonizing the light yellow powder obtained in the step 1) at high temperature under the nitrogen condition, wherein the heating rate is 3-5 ℃/min, calcining for 1-3h when the temperature is raised to 350-;
3) adding the carbonized product obtained in the step 2) into a hydrofluoric acid solution, stirring for 3-12h at room temperature, filtering, and drying the washed product to obtain the nitrogen-doped hierarchical pore carbon spheres;
the nitrogen source precursor is selected from one or more of 2, 6-diaminopyridine, 2-aminopyridine and 2-amino-6-methylpyridine; the surfactant is selected from one or more of nonionic surfactants F127, F108 and P123; the silicon source precursor is selected from one or more of silane reagents TEOS, TMOS and BTEB.
2. The preparation method of the iron-nitrogen co-doped hierarchical pore carbon sphere is characterized by comprising the following specific steps:
1) dissolving a nitrogen source precursor, a surfactant and an iron source precursor in water, then adding a silicon source precursor and ethanol, and uniformly stirring at 10-40 ℃; adding 35-40wt% of formaldehyde aqueous solution to initiate polymerization, and continuously reacting for 1-15h at 10-40 ℃ to obtain milk white prepolymer; then transferring the mixture into a high-pressure reaction kettle, carrying out hydrothermal reaction for 12-24h at the temperature of 90-120 ℃, standing, washing, centrifuging, drying and grinding to obtain light yellow powder;
2) carbonizing the light yellow powder obtained in the step 1) at high temperature under the nitrogen condition, wherein the heating rate is 3-5 ℃/min, calcining for 1-3h when the temperature is raised to 350-;
3) adding the carbonized product obtained in the step 2) into a hydrofluoric acid solution, stirring for 3-12h at room temperature, and drying the filtered and washed product at 60-90 ℃ to obtain an iron-nitrogen co-doped hierarchical porous carbon sphere;
the nitrogen source precursor is selected from one or more of 2, 6-diaminopyridine, 2-aminopyridine and 2-amino-6-methylpyridine; the surfactant is selected from one or more of nonionic surfactants F127, F108 and P123; the silicon source precursor is selected from one or more of silane reagents TEOS, TMOS and BTEB.
3. The preparation method of the iron-nitrogen co-doped hierarchical pore carbon sphere is characterized by comprising the following specific steps:
1) dissolving a nitrogen source precursor and a surfactant in water, then adding a silicon source precursor and ethanol, and uniformly stirring at 10-40 ℃; adding 35-40wt% of formaldehyde water solution to initiate polymerization, and continuously reacting for 1-15h at 10-40 ℃ to obtain milk white prepolymer;
2) adding an iron source precursor into the prepolymer obtained in the step 1), and stirring for reaction for 1-8 h; then transferring the mixture into a high-pressure reaction kettle, carrying out hydrothermal reaction for 12-24h at 90-120 ℃, standing, washing, centrifuging, drying at 60-90 ℃, and grinding to obtain light yellow powder;
3) carbonizing the light yellow powder obtained in the step 2) at high temperature under the nitrogen condition, wherein the heating rate is 3-5 ℃/min, calcining for 1-3h when the temperature is raised to 350-;
4) adding the carbonized product obtained in the step 3) into a hydrofluoric acid solution, stirring at room temperature for 3-12h, and drying the filtered and washed product at 60-90 ℃ to obtain the iron-nitrogen co-doped hierarchical porous carbon spheres;
the nitrogen source precursor is selected from one or more of 2, 6-diaminopyridine, 2-aminopyridine and 2-amino-6-methylpyridine; the surfactant is selected from one or more of nonionic surfactants F127, F108 and P123; the silicon source precursor is selected from one or more of silane reagents TEOS, TMOS and BTEB.
4. The preparation method according to claim 2 or 3, wherein the iron source precursor is selected from one or more of iron acetylacetonate, iron phthalocyanine and iron acetate.
5. The method according to any one of claims 1 to 3, wherein the mass ratio of the nitrogen source precursor to the surfactant is 3:0.8 to 4; the mass ratio of the surfactant to the silicon source precursor is 0.1-2: 2.325; the mass ratio of the ethanol to the surfactant is 1.76-8.78: 1; the mass ratio of the surfactant to the water is 0.2-1: 100; the mass ratio of the nitrogen source precursor to the formaldehyde is 0.5-1.6: 1.625.
6. The method according to claim 2 or 3, wherein the iron source precursor is added in an amount of not more than 16% by mass based on the mass of the nitrogen source precursor.
7. The application of the nitrogen-doped or iron-nitrogen-co-doped hierarchical porous carbon spheres prepared by the method according to any one of claims 1 to 3 in electrocatalytic oxygen reduction reaction.
8. The use according to claim 7, wherein the specific conditions of the electrocatalytic oxygen reduction reaction are as follows: mixing nitrogen-doped or iron-nitrogen-codoped hierarchical porous carbon spheres with ethanol and Nafion solution, performing ultrasonic dispersion, then dropwise coating on a glassy carbon electrode, drying to obtain a working electrode, introducing oxygen into saturated alkaline electrolyte, and performing electrocatalytic oxygen reduction reaction by using a three-electrode system, wherein the platinum electrode is a counter electrode, and Ag/AgCl is a reference electrode.
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| CN104624154A (en) * | 2015-01-23 | 2015-05-20 | 南开大学 | Preparation method and application of iron-nitrogen co-doped porous carbon sphere material |
| CN106517136A (en) * | 2016-10-26 | 2017-03-22 | 青岛科技大学 | Method for preparing iron/nitrogen-codoped ordered mesoporous carbon material |
| CN106744805A (en) * | 2017-01-25 | 2017-05-31 | 贵州大学 | Ultra-large aperture meso-porous carbon material of situ Nitrogen Doping and preparation method thereof |
| CN107746049A (en) * | 2017-10-13 | 2018-03-02 | 齐齐哈尔大学 | Melamine route for steam synthesizes rich nitrogen ordered mesoporous carbon material |
| CN110407194A (en) * | 2019-08-02 | 2019-11-05 | 武汉理工大学 | The hollow Nano carbon balls of three-dimensional porous N doping and its controllable method for preparing and application |
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| CN104624154A (en) * | 2015-01-23 | 2015-05-20 | 南开大学 | Preparation method and application of iron-nitrogen co-doped porous carbon sphere material |
| CN106517136A (en) * | 2016-10-26 | 2017-03-22 | 青岛科技大学 | Method for preparing iron/nitrogen-codoped ordered mesoporous carbon material |
| CN106744805A (en) * | 2017-01-25 | 2017-05-31 | 贵州大学 | Ultra-large aperture meso-porous carbon material of situ Nitrogen Doping and preparation method thereof |
| CN107746049A (en) * | 2017-10-13 | 2018-03-02 | 齐齐哈尔大学 | Melamine route for steam synthesizes rich nitrogen ordered mesoporous carbon material |
| CN110407194A (en) * | 2019-08-02 | 2019-11-05 | 武汉理工大学 | The hollow Nano carbon balls of three-dimensional porous N doping and its controllable method for preparing and application |
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