CN107583662B - Oxygen reduction catalyst and preparation method and application thereof - Google Patents
Oxygen reduction catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an oxygen reduction catalyst, comprising: a hollow nitrogen-doped carbon sphere having a shell; and transition metal nanoparticles embedded in the shell. The oxygen reduction catalyst provided by the invention has uniform transition metal nanoparticle-nitrogen doped active center, and appropriate pore diameter and high specific surface area of mesoporous pore canal, and is beneficial to the transmission of reactants and products in the oxygen reduction process, so that the oxygen reduction catalyst has high-efficiency oxygen reduction catalytic performance and excellent stability. The invention also discloses a preparation method of the oxygen reduction catalyst, which comprises the following steps: dispersing a microsphere template in an alkaline solution to obtain a first mixture; adding a nitrogen-doped carbon source and a transition metal salt into the first mixture, and polymerizing the nitrogen-doped carbon source to obtain a second mixture; the second mixture is dried and calcined in a protective gas to obtain the oxygen reduction catalyst. The invention also discloses the application of the oxygen reduction catalyst in a cathode of a fuel cell.
Description
Technical Field
The invention belongs to the technical field of oxygen reduction catalysts, and particularly relates to an oxygen reduction catalyst and a preparation method and application thereof.
Background
A fuel cell is a power generation device that directly converts chemical energy of fuel into electrical energy with high efficiency and without pollution, and is known as a fourth generation power generation technology following water power, fire power, nuclear energy due to its advantages of high energy conversion rate, low environmental pollution, short start-up time, and diversified fuels.
The cathode of the fuel cell has a relatively slow oxygen reduction reaction rate, and in practical applications, a catalyst with high catalytic activity must be used to increase the oxygen reduction rate, and generally, platinum nanoparticles supported on a carbon material are used as the catalyst. However, the above-mentioned catalyst belongs to a noble metal platinum-based catalyst, and has problems of high price, scarce reserves in the natural world, poor stability in an alkaline environment, and the like, which greatly limits the large-scale commercial application of fuel cells.
In recent years, transition metal and nitrogen-doped carbon materials show excellent electrocatalytic performance due to the characteristics of multiple active centers and high catalytic activity, and are expected to replace the noble metal platinum-based catalyst, so that the transition metal and nitrogen-doped carbon materials are widely applied to the development of fuel cells.
The prior preparation method of the transition metal and nitrogen-doped carbon material generally comprises the step of directly calcining transition metal salt, nitrogen-containing organic matters and carbon precursors at high temperature, and the preparation method has the defects of easy agglomeration, low surface area, difficult repetition and the like although the process is simple.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an oxygen reduction catalyst, a preparation method and an application thereof, wherein the oxygen reduction catalyst has high-efficiency oxygen reduction catalytic performance and excellent stability, and the preparation method is simple and can be applied to the oxygen reduction reaction of a cathode in a fuel cell.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
an oxygen reduction catalyst comprising: a hollow nitrogen-doped carbon sphere having a shell; and transition metal nanoparticles embedded in the shell.
Furthermore, the shell is provided with a mesoporous pore canal which is communicated with the inside and the outside; the aperture of the mesoporous pore canal is 2 nm-20 nm.
Further, the transition metal nanoparticles are selected from any one of cobalt nanoparticles, manganese nanoparticles and nickel nanoparticles.
Further, the particle size of the hollow nitrogen-doped carbon spheres is 50 nm-300 nm; the thickness of the shell is 5 nm-30 nm; the particle size of the transition metal nano-particles is 0.2 nm-20 nm.
Further, the oxygen reduction catalyst had a specific surface area of 150m2/g～660m2/g。
It is another object of the present invention to provide a method for preparing the oxygen-reducing catalyst as described above, comprising: dispersing a microsphere template in an alkaline solution to obtain a first mixture; adding a nitrogen-doped carbon source and a transition metal salt into the first mixture, and polymerizing the nitrogen-doped carbon source to obtain a second mixture; the second mixture is dried and calcined in a protective gas to obtain the oxygen reduction catalyst.
The transition metal salt is selected from any one of cobalt salt, manganese salt and nickel salt, wherein the cobalt salt is selected from at least one of cobalt nitrate, cobalt acetate, cobalt sulfate and cobalt chloride, the manganese salt is selected from at least one of manganese nitrate, manganese acetate, manganese sulfate and manganese chloride, the nickel salt is selected from at least one of nickel nitrate, nickel acetate, nickel sulfate and nickel chloride, and the nitrogen-doped carbon source is selected from any one of dopamine, α -methyldopamine and α -hydroxydopamine.
Further, the mass ratio of the nitrogen-doped carbon source to the transition metal salt is 1:2 to 1: 0.2; the mass ratio of the nitrogen-doped carbon source to the microsphere template is 1: 5-1: 1.
Further, the microsphere template is selected from any one of a polystyrene microsphere template, a polyacrylate microsphere template and a polyurethane microsphere template; the alkaline solution is at least one of aqueous ammonia solution, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution and aqueous tris (hydroxymethyl) aminomethane solution; wherein the concentration of the alkaline solution is 0.1-2 mol/L.
Further, the concentration of the microsphere template in the first mixture is 1 mg/mL-10 mg/mL.
Further, after dispersing the microsphere template into the alkaline solution, performing ultrasonic treatment for 0.5 to 1 hour; adding a nitrogen-doped carbon source and a transition metal salt into the first mixture, and stirring at 0-80 ℃ for 8-48 h; the specific method for drying and calcining the second mixture comprises the following steps: raising the temperature to 700-1000 ℃ according to the heating rate of 1-10 ℃/min, and keeping the temperature for 0.5-5 h.
It is also an object of the present invention to provide the use of an oxygen reduction catalyst as described above in the cathode of a fuel cell.
The invention has the beneficial effects that:
the oxygen reduction catalyst provided by the invention has uniform transition metal nanoparticles-nitrogen-doped active centers, and appropriate pore diameters and high specific surface areas of mesoporous channels; the hollow carbon spheres have high specific surface area and can fully expose the catalytic active centers on the surface of the oxygen reduction catalyst; the hollow structure of the hollow carbon sphere and the mesoporous pore canal on the shell are beneficial to the transmission of reactants and products in the oxygen reduction process and promote the catalytic reaction; moreover, the hollow carbon spheres are highly graphene-based, so that the conductivity of the material can be increased; the active center formed by transition metal and nitrogen element is uniformly dispersed on the shell, which is beneficial to the maximum utilization of the active center; therefore, the oxygen reduction catalyst has excellent oxygen reduction electrocatalytic performance when applied to an oxygen reduction reaction of a cathode in a fuel cell. Meanwhile, the preparation method of the oxygen reduction catalyst is simple, and raw materials are easy to obtain.
Drawings
The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a TEM photograph of an oxygen-reducing catalyst according to example 1 of the present invention;
FIG. 2 is a photograph of an HADF-STEM and a photograph of the distribution of carbon, nitrogen and cobalt in the oxygen-reducing catalyst according to example 1 of the present invention;
FIG. 3 is an XRD photograph of an oxygen reduction catalyst according to example 1 of the present invention;
FIG. 4 is a Raman spectrum of an oxygen-reducing catalyst according to example 1 of the present invention;
FIG. 5 is a thermogravimetric analysis curve of an oxygen reduction catalyst according to example 1 of the present invention;
fig. 6 is a nitrogen adsorption desorption curve and a pore size distribution diagram of an oxygen reduction catalyst according to example 1 of the present invention;
FIG. 7 is a TEM photograph of a polystyrene microsphere template according to example 2 of the present invention;
FIG. 8 is a TEM photograph of a second mixture according to example 2 of the present invention;
FIG. 9 is a photograph of the HADF-STEM and a photograph of the distribution of carbon, nitrogen and cobalt in the second mixture according to example 2 of the present invention;
FIG. 10 is a cyclic voltammogram of an oxygen reduction catalyst according to example 3 of the present invention;
FIG. 11 is a comparison of polarization curves for an oxygen-reducing catalyst according to example 3 of the present invention and a catalyst of comparative example 1;
fig. 12 is a graph comparing constant voltage curves of the oxygen-reducing catalyst of example 3 according to the present invention and the catalyst of comparative example 1.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
It will be understood that, although the terms "first," "second," etc. may be used herein to describe various substances, these substances should not be limited by these terms. These terms are only used to distinguish one substance from another.
Example 1
The embodiment discloses an oxygen reduction catalyst, which comprises hollow nitrogen-doped carbon spheres with shells and transition metal nano-particles embedded in the shells; the shell is also provided with mesoporous channels penetrating through the inside and the outside, and the average pore diameter of the mesoporous channels is 3.8 nm.
Specifically, in the present embodiment, the transition metal nanoparticles are cobalt nanoparticles, and the average particle diameter of the cobalt nanoparticles is 20 nm.
More specifically, the particle size of the hollow nitrogen-doped carbon spheres is 290nm, the thickness of the shell is 20 nm; the specific surface area of the oxygen reduction catalyst is 340m2/g。
It is worth to be noted that the material of the shell in the oxygen reduction catalyst of the present embodiment is nitrogen-doped carbon, which has a graphene-like structure; that is, when the shell is in an unfolded state, the shell is a two-dimensional layered structure, and the shell is formed by stacking a plurality of layers of the two-dimensional layered structure, the transition metal nanoparticles are sandwiched by the plurality of layers of the two-dimensional layered structure, and when the transition metal nanoparticles are in a hollow spherical shape, the transition metal nanoparticles are the oxygen reduction catalyst.
The oxygen reduction catalyst of this example was subjected to transmission electron microscope scanning test (TEM for short), high-angle annular dark field scanning transmission electron microscope test (HADF-STEM for short), carbon, nitrogen, and cobalt element distribution test, X-ray diffraction test (XRD for short), raman spectroscopy test, thermogravimetric analysis, and specific surface test, and the test results are shown in fig. 1 to fig. 6, respectively. As can be seen from fig. 1, the oxygen reduction catalyst includes a hollow sphere having a shell, and transition metal nanoparticles embedded in the shell; as can be seen from FIG. 2, the oxygen reduction catalyst is composed of elements such as carbon, nitrogen, cobalt and the like, and is uniformly distributed; as can be seen from fig. 3, XRD phase analysis corresponds to the elemental cobalt (i.e., cobalt nanoparticles embedded in the shell) contained in the oxygen reduction catalyst; as can be seen from fig. 4, the oxygen reduction catalyst has typical D and G peaks of the carbon material, and the smaller intensity ratio of the D peak to the G peak (about 1) indicates that the carbon in the oxygen reduction catalyst is highly graphene-oxidized during the high-temperature treatment; as can be seen from fig. 5, the residual mass percentage of the oxygen reduction catalyst after thermogravimetric analysis under air condition is 16.1%, and the mass percentage of the oxygen reduction catalyst actually having cobalt simple substance (i.e. cobalt nanoparticles) is calculated to be 11.8%; as can be seen from FIG. 6, the adsorption-desorption curve has a hysteresis loop, which proves that the oxygen reduction catalyst has a mesoporous channel structure with a pore diameter of about 3.8 nm.
Example 2
Example 2 is intended to describe in detail the method of preparing the oxygen reduction catalyst in example 1 above.
The preparation method of the oxygen reduction catalyst according to the present example includes the steps of:
in step S1, the microsphere template is dispersed in an alkaline solution to obtain a first mixture.
In this embodiment, the microsphere template is specifically a polystyrene microsphere template, and the alkaline solution is tris aqueous solvent; the invention is not limited to the template, and the microsphere template can also be other templates such as polyacrylate microsphere template, polyurethane microsphere template and the like, and only the material can be heated and decomposed at a higher temperature (such as 700-1000 ℃); the alkaline solution may be at least one of an aqueous ammonia solution, an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution, or a mixed solution of a tris aqueous solvent and at least one of the above alkaline solutions; the concentration of the alkaline solution is controlled to be 0.1-2 mol/L.
Specifically, the dosage of the polystyrene microsphere template is 1g, the concentration of the tris aqueous solvent is 10mmol/L, and the dosage is 200mL, so that the concentration of the microsphere template in the first mixture is about 10 mg/mL; generally, the concentration of the microsphere template is ensured to be 1 mg/mL-10 mg/mL.
Preferably, after dispersing the microsphere template in the alkaline solution, the ultrasound may be performed for 0.5h to 1h, preferably 0.5h, to make the microsphere template dispersed more uniformly, thereby obtaining a uniform first mixture.
The polystyrene microsphere template of this example was subjected to a scanning test with a transmission electron microscope, and the test results are shown in fig. 7. As can be seen from FIG. 7, the polystyrene microspheres are uniform and have a particle size of about 270 nm.
In step S2, a nitrogen-doped carbon source and a transition metal salt are added to the first mixture, and the nitrogen-doped carbon source is polymerized to obtain a second mixture.
Specifically, the nitrogen-doped carbon source in this embodiment is dopamine, and the transition metal salt is cobalt nitrate; wherein the dosage of the dopamine and the cobalt nitrate is 400mg, so that the mass ratio of the nitrogen-doped carbon source to the transition metal salt is 1: 1.
Preferably, after adding the nitrogen-doped carbon source and the transition metal salt into the first mixture, stirring for 8-48 h at 0-80 ℃; in this example, the stirring temperature was 25 ℃ and the stirring time was 24 hours.
It should be noted that the alkaline environment provided by the first mixture can promote polymerization of dopamine to form polydopamine, thereby chelating cobalt ions in cobalt nitrate, and thus ensuring uniform dispersion of cobalt ions in the second mixture, but the nitrogen-doped carbon source of the present invention is not limited to the dopamine, and the substance capable of serving as the nitrogen-doped carbon source may be α -methyldopamine, α -hydroxydopamine, etc., and only needs to ensure that the nitrogen-doped carbon source can serve as the nitrogen-doped carbon source, and can polymerize under alkaline conditions, thereby chelating transition metal ions in the transition metal salt added to the first mixture.
The second mixture of this example was subjected to a transmission electron microscope scanning test, a high-angle annular dark field scanning transmission electron microscope test, and a carbon, nitrogen, and cobalt element distribution test, and the test results are shown in fig. 8 and fig. 9, respectively. As can be seen from FIG. 8, the second mixture was obtained from nitrogen-doped carbon source polymerization coated polystyrene microspheres, which were uniform in size and had a particle size of about 330 nm; as can be seen from fig. 9, the second mixture is composed of carbon, nitrogen, cobalt, and the like, and the three elements are uniformly distributed.
In step S3, the second mixture is dried and calcined in a protective gas to obtain an oxygen-reducing catalyst.
Specifically, the second mixture is dried to obtain a solid; in argon atmosphere, heating the solid to 700-1000 ℃ at a heating rate of 1-10 ℃/min, and keeping the temperature for 0.5-5 h, preferably to 900 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 2 h; finally, the temperature was lowered to room temperature (about 25 ℃ C.) and the mixture was ground to obtain the oxygen reduction catalyst as described in example 1.
Example 3
Example 3 is intended to describe the use of the oxygen reduction catalyst described in example 1 in the cathode of a fuel cell.
The application of the oxygen reduction catalyst according to the present embodiment in the cathode of the fuel cell is specifically referred to the following steps:
in step Q1, an oxygen reduction catalyst is dispersed in an aqueous solution of ethanol to obtain a first solution.
Specifically, this example used 5mg of the oxygen reduction catalyst in example 1, and the aqueous solution of ethanol for dispersing the oxygen reduction catalyst was prepared by mixing 765. mu.L of water and 200. mu.L of ethanol.
In step Q2, a perfluorosulfonic acid solution is added to the first solution to obtain a first slurry.
Specifically, the amount of the perfluorosulfonic acid solution used was 35. mu.L.
Preferably, the first slurry obtained is more uniform by ultrasonication for 40min after the addition of the perfluorosulfonic acid solution to the first solution.
In step Q3, the first slurry is applied to a rotating disk electrode and, after being completely dried, the oxygen reduction catalyst is subjected to oxygen reduction electrocatalysis on the rotating disk electrode under alkaline conditions.
Specifically, the amount of the first slurry used was 4 μ L, and the diameter of the rotating disk electrode was 3 mm; the alkaline condition is specifically defined as the condition in which O is2Saturated 0.1mol/L KOH aqueous solution was used as the electrolyte.
More specifically, the electrochemical workstation is adopted to measure the oxygen reduction electrocatalytic performance of the oxygen reduction catalyst, and a cyclic voltammetry curve, a polarization curve and a constant voltage curve are respectively tested. The test conditions of the cyclic voltammogram were: the scanning speed is 5mV/s, and the voltage range is 0.375V-0.975V; the test conditions for the polarization curve were: the scanning speed is 5mV/s, and the voltage range is 0.3V-1.1V; the test conditions for the constant voltage curve were: the constant voltage was 0.7V and the test time was 60000 s. The test results are shown in fig. 10-12, respectively. As can be seen in FIG. 10, the oxygen reduction catalyst is in N2No reaction takes place in a saturated 0.1mol/L aqueous KOH solution, but in O2Obvious oxygen reduction peaks appear in a saturated 0.1mol/L KOH aqueous solution, and the peak positions are higher, which shows that the oxygen reduction catalyst has good oxygen reduction catalytic performance; as can be seen in conjunction with FIG. 11, it peaksThe potential and the half-wave potential are respectively 0.940V and 0.851V, which shows that the oxygen reduction catalyst has lower overpotential in the catalytic oxygen reduction reaction, and is beneficial to reducing the energy consumption of the catalytic reaction; as can be seen from FIG. 12, the constant voltage test of 60000s at a voltage of 0.7V showed only a 3.9% decrease in current density, indicating that the oxygen reduction catalyst had good stability in 0.1mol/L KOH in water.
Comparative example 1
Comparative example 1 is intended to illustrate the advantages of the oxygen reduction catalyst of example 3 over the prior art catalyst for use in the cathode of a fuel cell by comparison with example 3.
The prior art catalyst selected for this comparative example was a 20% commercial platinum carbon catalyst (i.e., a platinum carbon catalyst with a Pt mass percent of 20%).
The polarization curve and the constant voltage curve were tested according to the method of example 3, with respect to the second solution and the second slurry obtained, respectively, under the test conditions described in example 3, and the test results are shown in fig. 11 and 12, respectively. As can be seen from fig. 11, the peak-onset potential and the half-wave potential of the 20% commercial platinum-carbon catalyst were 1.080V and 0.890V, respectively, and comparing the polarization curves of the oxygen-reducing catalyst of example 3 and the catalyst of comparative example 1 in fig. 11, it can be seen that the oxygen-reducing catalyst has the peak-onset potential and the half-wave potential close to those of the 20% commercial platinum-carbon catalyst, indicating that the catalytic performance of the oxygen-reducing catalyst is close to that of the 20% commercial platinum-carbon catalyst, and the purpose of replacing the expensive platinum-carbon catalyst with the inexpensive catalyst can be achieved; as can be seen from fig. 12, when the constant voltage test of 60000s was performed at a voltage of 0.7V, the current density of the catalyst in the present comparative example was reduced by 13.5%, and the reduction amount of the current density of the oxygen-reducing catalyst in example 3 was greatly reduced, indicating that the stability of the oxygen-reducing catalyst in the present example was greatly improved as compared with the catalyst in the prior art.
Example 4
In the description of embodiment 4, the same points as those of embodiment 1 will not be described again, and only the differences from embodiment 1 will be described. Example 4 difference from example 1Characterized in that the average pore diameter of the mesoporous pore canal is 2 nm; the average particle size of the manganese nanoparticles is 0.5 nm; the particle size of the hollow nitrogen-doped carbon spheres is 50nm, and the thickness of the shell is 5 nm; the specific surface area of the oxygen reduction catalyst was 150m2/g。
Example 5
Example 5 is intended to describe in detail the method of preparing the oxygen reduction catalyst in the above example 4.
In the description of embodiment 5, the same points as those of embodiment 2 will not be described again, and only the differences from embodiment 2 will be described. Example 5 is different from example 2 in that, in step S2, the transition metal salt is manganese nitrate; wherein the dosage of the dopamine is 400mg, and the dosage of the manganese nitrate is 200mg, so that the mass ratio of the nitrogen-doped carbon source to the transition metal salt is 1: 0.5. The oxygen reduction catalyst as described in example 4 was prepared as otherwise described with reference to example 2.
Example 6
In the description of embodiment 6, the same points as those of embodiment 1 will not be described again, and only the differences from embodiment 1 will be described. Example 6 is different from example 1 in that the average pore diameter of the mesoporous channel is 20 nm; the average particle diameter of the nickel nanoparticles is 20 nm; the particle size of the hollow nitrogen-doped carbon spheres is 300nm, and the thickness of the shell is 30 nm; the specific surface area of the oxygen reduction catalyst was 660m2/g。
Example 7
Example 7 is intended to describe in detail the method for producing the oxygen reduction catalyst in the above example 6.
In the description of embodiment 7, the same points as those of embodiment 2 will not be described again, and only the differences from embodiment 2 will be described. Example 7 is different from example 2 in that, in step S2, the transition metal salt is nickel nitrate; wherein the dosage of the dopamine is 400mg, and the dosage of the nickel nitrate is 800mg, so that the mass ratio of the nitrogen-doped carbon source to the transition metal salt is 1: 2. The oxygen reduction catalyst as described in example 6 was prepared as otherwise described with reference to example 2.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will understand that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (8)
1. An oxygen reduction catalyst, comprising:
the hollow nitrogen-doped carbon sphere comprises a shell, wherein the shell is provided with a mesoporous pore canal which is communicated with the inside and the outside, and the aperture of the mesoporous pore canal is 2 nm-20 nm;
and transition metal nanoparticles embedded in the shell, wherein the transition metal nanoparticles are selected from any one of cobalt nanoparticles, manganese nanoparticles and nickel nanoparticles;
wherein the particle size of the hollow nitrogen-doped carbon spheres is 50 nm-300 nm; the thickness of the shell is 5 nm-30 nm; the particle size of the transition metal nano-particles is 0.2 nm-20 nm; the oxygen reduction catalyst has a specific surface area of 150m2/g～660m2/g。
2. The method of preparing an oxygen-reducing catalyst according to claim 1, comprising:
dispersing a microsphere template in an alkaline solution to obtain a first mixture;
adding a nitrogen-doped carbon source and a transition metal salt into the first mixture, and polymerizing the nitrogen-doped carbon source to obtain a second mixture;
the second mixture is dried and calcined in a protective gas to obtain the oxygen reduction catalyst.
3. The preparation method according to claim 2, wherein the transition metal salt is selected from any one of cobalt salt, manganese salt and nickel salt, wherein the cobalt salt is selected from at least one of cobalt nitrate, cobalt acetate, cobalt sulfate and cobalt chloride, the manganese salt is selected from at least one of manganese nitrate, manganese acetate, manganese sulfate and manganese chloride, the nickel salt is selected from at least one of nickel nitrate, nickel acetate, nickel sulfate and nickel chloride, and the nitrogen-doped carbon source is selected from any one of dopamine, α -methyldopamine and α -hydroxydopamine.
4. The production method according to claim 2 or 3, wherein the mass ratio of the nitrogen-doped carbon source to the transition metal salt is 1:2 to 1: 0.2; the mass ratio of the nitrogen-doped carbon source to the microsphere template is 1: 5-1: 1.
5. The preparation method according to claim 4, wherein the microsphere template is selected from any one of polystyrene microsphere template, polyacrylate microsphere template and polyurethane microsphere template;
the alkaline solution is at least one of aqueous ammonia solution, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution and aqueous tris (hydroxymethyl) aminomethane solution; wherein the concentration of the alkaline solution is 0.1-2 mol/L.
6. The method of claim 2, wherein the concentration of the microsphere template in the first mixture is 1mg/mL to 10 mg/mL.
7. The preparation method of claim 2, wherein the microsphere template is dispersed in the alkaline solution and then subjected to ultrasonic treatment for 0.5 to 1 hour;
adding a nitrogen-doped carbon source and a transition metal salt into the first mixture, and stirring at 0-80 ℃ for 8-48 h;
the specific method for drying and calcining the second mixture comprises the following steps: raising the temperature to 700-1000 ℃ according to the heating rate of 1-10 ℃/min, and keeping the temperature for 0.5-5 h.
8. Use of an oxygen reduction catalyst according to claim 1 in the cathode of a fuel cell.
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| Efficient and reusable Co/nitrogen doped hollow carbon sphere;Isaac Nongwe et al.;《Applied Catalysis A:General》;20130624;第466卷;第1-8页 * |
| Nitrogen-Doped Hollow Carbon Spheres as a Support for Platinum-Based Electrocatalysts;Carolina Galeano et al.;《Catalysis》;20140908;第4卷;第3856-3868页 * |
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