CN110492114B - Nitrogen-doped porous carbon-oxygen reduction catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped porous carbon-oxygen reduction catalyst and preparation method and application thereof Download PDFInfo
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- CN110492114B CN110492114B CN201910770490.6A CN201910770490A CN110492114B CN 110492114 B CN110492114 B CN 110492114B CN 201910770490 A CN201910770490 A CN 201910770490A CN 110492114 B CN110492114 B CN 110492114B
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract
The invention relates to a nitrogen-doped porous carbon-oxygen reduction catalyst, a preparation method and application thereof, and belongs to the field of fuel cell catalyst materials. A preparation method of a nitrogen-doped porous carbon-oxygen reduction catalyst comprises the steps of mixing polyvinylpyrrolidone and a triblock copolymer (F127) of polyethylene oxide-polypropylene oxide-polyethylene oxide, performing hydrothermal reaction to obtain an intermediate product, and drying the intermediate product to obtain a transparent film-shaped substance; and carbonizing the transparent film-shaped substance under the condition of nitrogen, washing, drying and grinding the obtained product to obtain the product. The method for preparing the nitrogen-doped nano hollow capsule-shaped porous carbon material has the advantages of simple operation, less flow, less equipment investment and good repeatability, and is convenient for solving the problem of difficult large-scale production.
Description
Technical Field
The invention relates to a nitrogen-doped porous carbon-oxygen reduction catalyst, a preparation method and application thereof, and belongs to the field of fuel cell catalyst materials.
Background
In recent years, energy shortage and environmental pollution are two major problems facing human beings, a replaceable new energy is searched, and a fuel cell serving as an energy conversion device has the advantages of high energy conversion rate, environmental friendliness and the like. The oxygen reduction reaction at the cathode of the fuel cell plays a critical role in the fuel cell due to its slow kinetic control step which limits the reaction speed of the fuel cell. While conventional Pt-based materials are the most practical and effective electrocatalysts for oxygen reduction reactions, they are hampered by high cost and susceptibility to poisoning in fuel cell industrialization. Therefore, the development of inexpensive, highly efficient, highly tolerant and stable electrocatalysts is a compelling research.
The doped heteroatom can destroy the electric neutrality of the carbon material and increase the adsorption position and oxygen reduction site of oxygen molecules. Therefore, heteroatom-doped carbon materials have received much attention. The radius of N is larger than that of carbon, the electronegativity is slightly smaller than that of carbon, and the N is easier to combine with carbon than other heteroatoms such as phosphorus, sulfur and the like. The nitrogen source is derived from pyrrole nitrogen, and the pyrrole nitrogen has remarkable improvement on catalytic performance and has more remarkable improvement performance than heteroatoms such as phosphorus, sulfur and the like. When N is doped with carbon, the interaction between the nitrogen atoms and the surrounding C atoms results in a redistribution of charge density and spin density, and then creates some active sites on the surface of the carbon material with either abundant or absent electrons. Therefore, the electron binding performance of the carbon material can be improved by doping nitrogen, and the catalytic activity is improved. However, the existing nitrogen-doped porous carbon-oxygen reduction catalyst experiment mainly takes an MgO hard template as a main part, the preparation process is complicated, and the hard template needs to be removed.
Disclosure of Invention
In order to search for an alternative catalyst and solve the problems of high preparation cost and complex preparation process of the existing catalyst, the invention provides a preparation method of a nitrogen-doped nano hollow capsule-shaped porous carbon-oxygen reduction catalyst, which has a simple preparation process.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a nitrogen-doped porous carbon oxygen reduction catalyst, which comprises the steps of mixing polyvinylpyrrolidone (PVP) and a triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide, carrying out hydrothermal self-assembly to obtain an intermediate product, drying the intermediate product, carbonizing, washing, drying and grinding the obtained product, and thus obtaining the nitrogen-doped porous carbon oxygen reduction catalyst.
In the preparation method, the dosage of the polyvinylpyrrolidone is 10-30% of the mass of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
Preferably, the polyvinylpyrrolidone is used in an amount of 10% by mass of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
The hydrothermal self-assembly reaction conditions in the preparation method are as follows: and keeping the temperature at 25-100 ℃ for 2-24 h.
In the above preparation method, Zn (OH) is added before hydrothermal self-assembly reaction2，Zn(OH)2The mass ratio of the block copolymer to the triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide is 1-2: 4.
In the preparation method, the carbonization conditions are as follows: under the nitrogen atmosphere, heating to 500-1000 ℃ at the heating rate of 2-5 ℃/min, preserving the heat for 2-6 h, and then cooling to the room temperature along with the furnace.
In the above preparation method, the washing is: soaking the mixture in 1-8 mol/LHCl solution, centrifuging the mixture for 5-10 min at 2500-4000 r/min by using deionized water, repeatedly centrifuging the mixture until the mixture is neutral, and then centrifugally cleaning the mixture by using absolute ethyl alcohol.
Preferably, the HCl solution used is a 2mol/LHCl solution.
The invention also provides a nitrogen-doped porous carbon-oxygen reduction catalyst, which is prepared by the preparation method, and the catalyst is a material with a nano hollow capsule-shaped structure, and the specific surface area of the material is 100-2000 g/m2。
In a third aspect, the invention provides the use of the nitrogen-doped porous carbon-oxygen reduction catalyst as a fuel cell cathode catalyst material and a catalyst support material.
The invention has the beneficial effects that: the method selects and uses mature commercial raw materials from the aspect of cost, the triblock copolymer material only contains C, H, O, the functional group only contains hydroxyl, the carbon source is relatively friendly to the environment, the porous carbon shows a nano hollow capsule-shaped structure, an electric transfer path and an oxygen absorption site are more easily provided due to the large specific surface area of the porous carbon, and after N heteroatom is introduced, the active site is increased, and the catalytic performance is greatly improved.
The catalyst material prepared by the method is a three-dimensional porous material with high specific surface area, has good electrocatalytic performance, and obviously reduces the catalyst cost.
The method for preparing the nitrogen-doped porous carbon material has the advantages of simple operation, less flow, less equipment investment and good repeatability, and is convenient for solving the problem of large-scale production.
Drawings
FIG. 1 is a representation of example 1 of the present invention; (a) is an SEM image (200 nm on scale) of the nitrogen-doped porous carbon-oxygen reduction catalyst material prepared in example 1; FIGS. 1(b), (c) are TEM images of the nitrogen-doped porous carbon-oxygen reduction catalyst material prepared in example 1; FIG. 1(d) is an electron diffraction pattern of the nitrogen-doped porous carbon-oxygen reduction catalyst material prepared in example 1;
FIG. 2 is an XRD spectrum of the nitrogen-doped porous carbon-oxygen reduction catalyst material prepared in the comparative example and examples 1-3 of the present invention;
FIG. 3 is a Raman spectrum of the nitrogen-doped porous carbon-oxygen reduction catalyst material prepared in comparative example 1 and examples 1 to 3 of the present invention;
FIG. 4 is a full spectrum and C1s and N1s spectra of a nitrogen-doped porous carbon oxygen reduction catalyst material prepared in example 1; FIG. 4(a) XPS total spectrum, FIG. 4(b) C1s spectrum, FIG. 4(C) N1s spectrum;
FIG. 5 is a graph of test results; FIG. 5(a) is a polarization curve at 1600rpm for nitrogen-doped porous carbon oxygen reduction catalyst materials prepared in comparative example and inventive examples 1-3, FIG. 5(b) is a rotating disk test curve for example 1, FIG. 5(c) is a K-L curve for example 1, and FIG. 5(d) is a cycle life curve for example 2.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Comparative example
1) 4g of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (abbreviation: F127) 100ml of deionized water is added and stirred evenly to obtain clear and transparent solution.
2) Adding 1.6g of zinc hydroxide into the solution, transferring the solution into a reaction kettle, setting the hydrothermal temperature to 80 ℃, preserving the heat for 12 hours, taking out the solution, and drying the solution at 60 ℃ for 24 hours to obtain a transparent film-shaped substance.
3) Carbonizing the transparent film-shaped substance in a tube furnace filled with nitrogen, wherein the carbonizing procedure comprises the following steps: heating to 700 ℃ from room temperature at the heating rate of 2 ℃/min, preserving heat for 3h, then cooling to room temperature along with the furnace, and taking out; soaking the mixture in 2mol/LHCl solution, centrifuging the mixture for 5min at 4000r/min by using deionized water, repeatedly centrifuging the mixture to be neutral, then centrifugally cleaning the mixture by using absolute ethyl alcohol, drying and grinding the mixture.
Example 1
1) 4g of F127 is taken and added with 100ml of deionized water, and the mixture is stirred evenly to obtain clear and transparent solution.
2) Polyvinylpyrrolidone (PVP) 10% by mass of F127, i.e. 0.4g of PVP, was added and stirred uniformly to obtain a clear and transparent solution.
3) Adding 1.6g of zinc hydroxide into the solution, transferring the solution into a reaction kettle, setting the hydrothermal temperature at 80 ℃, preserving the heat for 12 hours, taking out the solution, and drying the solution at 60 ℃ for 24 hours to obtain a transparent film-shaped substance.
4) Carbonizing a transparent film-shaped substance in a tube furnace filled with nitrogen, wherein the carbonizing procedure comprises the following steps: heating to 700 ℃ from room temperature at the heating rate of 2 ℃/min, preserving heat for 3h, then cooling to room temperature along with the furnace, and taking out; soaking the mixture in 2mol/LHCl solution, centrifuging the mixture for 5min at 4000r/min by using deionized water, repeatedly centrifuging the mixture to be neutral, then centrifugally cleaning the mixture by using absolute ethyl alcohol, drying and grinding the mixture.
Example 2
1) 4g of F127 is taken and added with 100ml of deionized water, and the mixture is stirred evenly to obtain clear and transparent solution.
2) Polyvinylpyrrolidone (PVP) in an amount of 20% by mass of F127, i.e., 0.8g of PVP, was added thereto and stirred uniformly to obtain a clear and transparent solution.
3) Adding 1.6g of zinc hydroxide into the solution, transferring the solution into a reaction kettle, setting the hydrothermal temperature at 80 ℃, preserving the heat for 12 hours, taking out the solution, and drying the solution at 60 ℃ for 24 hours to obtain a transparent film-shaped substance.
4) Carbonizing the transparent film-shaped substance in a tube furnace filled with nitrogen, wherein the carbonizing procedure comprises the following steps: heating to 700 ℃ from room temperature at the heating rate of 2 ℃/min, preserving heat for 3h, then cooling to room temperature along with the furnace, and taking out; soaking the mixture in 2mol/LHCl solution, centrifuging the mixture for 5min at 4000r/min by using deionized water, repeatedly centrifuging the mixture to be neutral, then centrifugally cleaning the mixture by using absolute ethyl alcohol, drying and grinding the mixture.
Example 3
1) 4g of F127 is taken and added with 100ml of deionized water, and the mixture is stirred evenly to obtain clear and transparent solution.
2) Polyvinylpyrrolidone (PVP) 30% by mass of F127, i.e., 1.2g of PVP, was added and stirred uniformly to obtain a clear and transparent solution.
3) Adding 1.6g of zinc hydroxide into the solution, transferring the solution into a reaction kettle, setting the hydrothermal temperature at 80 ℃, preserving the heat for 12 hours, taking out the solution, and drying the solution at 60 ℃ for 24 hours to obtain a transparent film-shaped substance.
4) Carbonizing the transparent film-shaped substance in a tube furnace filled with nitrogen, wherein the carbonizing procedure comprises the following steps: heating to 700 ℃ from room temperature at the heating rate of 2 ℃/min, preserving heat for 3h, then cooling to room temperature along with the furnace, and taking out; soaking the mixture in 2mol/LHCl solution, centrifuging the mixture for 5min with deionized water at 4000r/min, repeatedly centrifuging the mixture to be neutral, then centrifugally cleaning the mixture with absolute ethyl alcohol, drying and grinding the cleaned mixture.
Example of effects: in order to explore the morphological characteristics and electrochemical properties of the prepared nitrogen-doped carbon catalyst, the prepared product is physically characterized by using SEM, XRD, XPS, Raman and other means, and is prepared into an electrode to test the corresponding electrochemical properties.
Fig. 1(a) is an SEM photograph (scale is 200nm) of the nitrogen-doped carbon catalyst prepared in example 1, and it can be seen from the SEM photograph of fig. 1(a) that the nitrogen-doped carbon catalyst is nanocapsule-like porous carbon at 50000 × magnification; from the TEM photographs of FIGS. 1(b) and (c), it can be seen that the interior has a hollow structure and a wall thickness of about 5nm, and FIG. 1(d) shows an electron diffraction ring thereof, indicating that the degree of graphitization is high.
Fig. 2(a) shows XRD spectra of the nitrogen-doped carbon catalysts prepared in comparative example and examples 1 to 3, in which (002) crystal face is graphitized carbon at 29 ° 2 θ, the doped amount of polyvinylpyrrolidone is different, the peak size is different, and the peak is the largest when the addition ratio is 10%. The result shows that the C-N-10% graphitization degree is high, and the conductivity is better. The Raman spectrum is shown in figure 3. The D peak appears at 1350cm-1 and the G peak appears at 1580 cm-1. As can be seen from the D peak and the G peak, the graphite has better defect degree and graphitization degree.
The full spectrum and the spectra of C1s and N1s of the material obtained in example 1 are shown in FIGS. 4(a) to (C). The existence of C and N elements can be clearly found in FIG. 4(a), and the existence of sp3-C, sp2-C and C-N can be analyzed in a spectrogram of C1 s. In the spectrum of N1s, pyrrole nitrogen and pyridine nitrogen can be analyzed, the proportion of pyrrole nitrogen is large when graphite nitrogen exists, and N is doped into carbon.
The prepared catalyst was coated on a glassy carbon electrode, and cyclic voltammetry, polarization curve, and stability tests were performed in a 0.1M KOH solution, and the test results are shown in fig. 5.
As can be seen from FIG. 5(a), in which F127 is a sample having a molecular weight Mn of 12600g/mol, Zn (OH) is not added2And a pure substance without PVP is added to produce the carbon material at high temperature. The polarization curves at 1600rpm for the different proportions of catalyst material show the optimum performance at a 10% added PVP proportion: the very good initial potential, very good limiting current density (example 1), it can be seen from fig. 5(b) that the limiting current density increases with increasing number of revolutions of the rotating disk for the catalyst of example 1, indicating that the diffusion layer is very thin, indicating that there are many active sites. FIG. 5(c) shows the number of transferred electrons at each potential, and then the number of transferred electrons was calculated to be 3.98 according to the K-L formula, which is favorable for four-electron transfer and suitable for oxygen reduction catalysts. As can be seen from fig. 5(d), the polarization curves tested after 2000 and 5000 cycles had little attenuation, indicating good stability.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (7)
1. A preparation method of a nitrogen-doped porous carbon-oxygen reduction catalyst is characterized by comprising the following steps: mixing polyvinylpyrrolidone and a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer F127, carrying out hydrothermal self-assembly to obtain an intermediate product, drying the intermediate product, carbonizing, washing, drying and grinding the obtained product to obtain the product;
the hydrothermal self-assembly reaction conditions are as follows: keeping the temperature for 2-24 h at 25-100 ℃;
the catalyst is a material with a nano hollow capsule-shaped structure.
2. The method for preparing a nitrogen-doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the method comprises the following steps: the dosage of the polyvinylpyrrolidone is 10-30% of the mass of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer F127.
3. The method for preparing a N-doped porous C/O reduction catalyst according to claim 1, wherein Zn (OH) is added before hydrothermal self-assembly reaction2，Zn(OH)2The mass ratio of the epoxy resin to the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer F127 is 1-2: 4.
4. The method for preparing a nitrogen-doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the carbonization conditions are as follows: under the nitrogen atmosphere, heating to 500-1000 ℃ at the heating rate of 2-5 ℃/min, preserving the heat for 2-6 h, and then cooling to the room temperature along with the furnace.
5. The method for preparing the nitrogen-doped porous carbon-oxygen reduction catalyst according to claim 1, wherein the washing is: soaking the fabric in 1-8 mol/L HCl solution, centrifuging the fabric for 5-10 min at 2500 r/min-4000 r/min with deionized water, repeatedly centrifuging the fabric to be neutral, and then centrifugally cleaning the fabric with absolute ethyl alcohol.
6. A nitrogen-doped porous carbon-oxygen reduction catalyst, which is prepared by the method of any one of claims 1 to 5.
7. The use of the nitrogen-doped porous carbon-oxygen reduction catalyst of claim 6 as a fuel cell cathode catalyst material.
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