CN115763850A - Preparation method and application of carbon-based oxygen reduction catalyst - Google Patents
Preparation method and application of carbon-based oxygen reduction catalyst Download PDFInfo
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- CN115763850A CN115763850A CN202211624396.8A CN202211624396A CN115763850A CN 115763850 A CN115763850 A CN 115763850A CN 202211624396 A CN202211624396 A CN 202211624396A CN 115763850 A CN115763850 A CN 115763850A
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Abstract
The invention relates to the technical field of electrocatalysis materials, in particular to a preparation method and application of a carbon-based oxygen reduction catalyst, and the preparation method of the carbon-based oxygen reduction catalyst mainly comprises the following steps: s1: attaching acetylacetone metal to the surface of a carbon-based carrier through a gas-phase impregnation method to obtain a carbon-based material attached with the acetylacetone metal; s2: replacing the ligand of the carbon-based material attached with the acetylacetone metal by a liquid phase replacement method using ammonia water, and then drying to obtain the carbon-based material attached with the metal coordination compound of the amino group; s3: the carbon-based oxygen reduction catalyst is obtained by subjecting the carbon-based material to high-temperature calcination to which the amino complex is attached. The preparation method has the advantages of simple process, lower preparation cost and better catalytic activity.
Description
Technical Field
The invention relates to the technical field of electrocatalytic materials, in particular to a preparation method and application of a carbon-based oxygen reduction catalyst.
Background
To alleviate the pressure on the demand of traditional energy sources, the development of renewable and sustainable energy sources to replace traditional energy sources has been imminent. Among the technologies, fuel cell technology has a very high reliability and can convert chemical energy into electrical energy electrochemically with high efficiency, thereby providing a clean, pollution-free and sustainable energy source. Fuel cells can be classified into the following categories according to the difference in electrolytes: proton exchange membrane fuel cells, solid oxide fuel cells, phosphoric acid fuel cells, methanol fuel cells, and molten carbonate fuel cells.
As a representative fuel cell, a pem fuel cell has been studied because of its advantages of low operating temperature, high energy density, low mass and small volume, etc., compared with other cells. However, the cathode kinetics are very slow and have a high potential, so that a catalyst is needed to assist the reaction. The commonly used catalysts are mainly divided into two types, including noble metal catalysts and non-noble metal catalysts, wherein commercial Pt/C belongs to noble metal catalysts and is one of the catalysts with the best catalytic performance, which is currently recognized, but the commercialization of fuel cells is hindered due to the small storage amount and high price of Pt.
In order to overcome the defects of the catalyst in price, people actively develop non-noble metal catalysts, and in recent years, people research and develop transition metal loaded on carbon materials to enable the transition metal loaded on the carbon materials to become one of the materials with the most potential to replace noble metal catalysts. For example, chinese patent No. CN113013428A discloses a preparation method and application of a Fe and Co bimetallic doped mesoporous carbon-oxygen reduction catalyst, but the preparation method adopted by the patent is complex, the catalytic performance is still inferior to that of the existing commercial Pt/C, and further improvement is needed.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method and application of a carbon-based oxygen reduction catalyst, wherein the preparation method of the oxygen reduction catalyst is simple in preparation process, lower in preparation cost and better in catalytic activity.
In order to achieve the technical effect, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a carbon-based oxygen reduction catalyst, wherein a carbon-based carrier is used as a carbon precursor, acetylacetone metal is used as a non-noble metal precursor, and ammonia water is used as a ligand displacer to prepare the carbon-based oxygen reduction catalyst.
Preferably, the iron acetylacetonate and the cobalt acetylacetonate are attached to the surface of the carbon-based support by a vapor phase impregnation method to obtain a carbon-based material to which the cobalt acetylacetonate and the iron acetylacetonate are attached, the ammonia water is further subjected to ligand replacement by a liquid phase replacement method for the carbon-based material to which the cobalt acetylacetonate and the iron acetylacetonate are attached to obtain a carbon-based material to which the aminocobalt/iron complex is attached, and finally the carbon-based material to which the aminocobalt/iron complex is attached is calcined at a high temperature to obtain the Fe-Co-N carbon-based oxygen reduction catalyst.
In a second aspect, the present invention provides a method for preparing a carbon-based oxygen reduction catalyst, comprising the steps of:
s1: attaching acetylacetone metal to the surface of a carbon-based carrier by a gas-phase impregnation method to obtain a carbon-based material attached with the acetylacetone metal;
s2: replacing the ligand of the carbon-based material attached with the acetylacetone metal by a liquid phase replacement method using ammonia water, and then drying to obtain the carbon-based material attached with the metal coordination compound of the amino group;
s3: the carbon-based oxygen reduction catalyst is obtained by subjecting the carbon-based material having the amino complex attached thereto to high-temperature calcination.
Further, the conditions of the gas phase impregnation method are high temperature and high pressure.
Further, the conditions of high temperature and high pressure are that the temperature is 150-250 ℃, the pressure is 0-3 MPa, and the processing time is 1-12 h.
Preferably, the conditions of high temperature and high pressure are that the temperature is 180-240 ℃, the pressure is 1-3 MPa, and the treatment time is 1.5-6 h.
Further, the acetylacetone metal in S1 is any one or a combination of more of iron acetylacetonate, cobalt acetylacetonate, and nickel acetylacetonate, and is preferably a mixture of iron acetylacetonate and cobalt acetylacetonate.
Further, the carbon-based carrier in S1 is any one of organic carbon and inorganic carbon.
Further, the carbon-based support may be selected from at least one of carbon black, carbon nanotubes, graphene, two-dimensional carbon sheets, and graphene oxide, or at least one of carbon black, carbon nanotubes, graphene, two-dimensional carbon sheets, and graphene oxide modified by a nitrogen-containing polymer.
Further, the concentration of ammonia water in the S2 is 25-28%, the replacement time is 0.5-10 h, the drying temperature is 60-100 ℃, and the drying time is 1-24 h.
Furthermore, the high-temperature calcination temperature in S3 is 300-1100 ℃, and the high-temperature calcination time is 0.2-3 h.
Further, the S3 further includes: after high-temperature calcination, removing larger metal particles in the carbonized product by acid liquor washing, washing for a plurality of times by ultrapure water, and drying to obtain the carbon-based oxygen reduction catalyst.
Further, the acid solution is any one of a sulfuric acid solution or a hydrochloric acid solution.
Further, the high-temperature calcination environment is an inert gas environment, and the inert gas environment is preferably any one of nitrogen or argon.
In a third aspect, the present invention further provides an application of the carbon-based oxygen reduction catalyst of the first aspect or the carbon-based oxygen reduction catalyst prepared by the preparation method of the second aspect, specifically including an application in a proton exchange membrane fuel cell, or an application in an oxygen reduction catalyst material used in a fuel cell or a metal-air battery.
Compared with the prior art, the invention has the following beneficial effects:
in a first aspect, the present invention provides a carbon-based oxygen reduction catalyst, in which a carbon-based carrier is used as a carbon precursor, iron acetylacetonate is used as an iron precursor, cobalt acetylacetonate is used as a cobalt precursor, and ammonia water is used as a nitrogen precursor, and when the carbon-based oxygen reduction catalyst is prepared, iron acetylacetonate and cobalt acetylacetonate are first attached to the surface of the carbon-based carrier by a vapor phase impregnation method to obtain a carbon-based material to which cobalt acetylacetonate and iron acetylacetonate are attached, and the ammonia water further performs ligand replacement on the carbon-based material to which cobalt acetylacetonate and iron acetylacetonate are attached by a liquid phase replacement method to obtain a carbon-based material to which an amino cobalt/iron complex is attached, and finally the carbon-based material to which the amino cobalt/iron complex is attached is calcined at a high temperature to obtain the carbon-based oxygen reduction catalyst.
In a second aspect, the invention also provides a preparation method of the carbon-based oxygen reduction catalyst, which abandons the traditional hydrothermal method for preparation and adopts a gas-phase impregnation method, so that the metal with catalytic activity can be quickly and conveniently loaded on the surface of the carbon-based carrier, the surface of the carrier is uniformly distributed with the minimum amount of the metal, the utilization rate of raw materials can be effectively improved, a metal complex with higher stability is obtained by a liquid-phase displacement method after the gas-phase impregnation method, a catalytic activity site is formed by a calcination process, and the stability of the catalyst is also improved.
Drawings
FIG. 1 is an SEM image of carbon nanotubes according to a first embodiment of the present invention;
FIG. 2 is an X-ray photoelectron spectrum of the N element provided by a second embodiment of the present invention;
FIG. 3 is a graph showing comparative results of oxygen reduction performance of carbon-based oxygen reduction catalysts prepared in examples 1 to 3 in a 0.1mol/LKOH solution, which are provided as experimental examples of a third embodiment of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only used as examples, and the protection scope of the present invention is not limited thereby. The examples are given solely for the purpose of illustration and are not intended to limit the scope of the invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents or apparatus used are those which are not specified by the manufacturer, are commercially available reagents and materials unless otherwise specified, and are not specified in the examples, and are carried out according to the conventional conditions or conditions recommended by the manufacturer.
Example 1
Referring to fig. 1, fig. 1 is an SEM image of the carbon nanotube used in the present embodiment;
this example is a first example of the present invention, and provides a carbon-based oxygen reduction catalyst prepared by the following method:
s1: weighing 0.5g of carbon nano tube and 1g of iron acetylacetonate by using a high-temperature high-pressure gas-phase impregnation method, placing the carbon nano tube and the iron acetylacetonate in a high-pressure hydrothermal reaction kettle, and impregnating for 1.5 hours at the temperature of 180 ℃ under the pressure of 1MPa to obtain a carbon-based material attached with the iron acetylacetonate;
s2: soaking the carbon-based material attached with the ferric acetylacetonate in an ammonia water solution with the concentration of 25% for 6 hours, and then drying at the temperature of 70 ℃ for 12 hours to obtain the carbon-based material attached with the amino iron coordination compound;
s3: and (3) drying the carbon-based carrier attached with the amino iron coordination compound, transferring the carbon-based carrier into a porcelain boat, placing the porcelain boat into a tubular furnace, and carbonizing the porcelain boat for 0.5h at the high temperature of 700 ℃ in an argon atmosphere. Naturally cooling to room temperature, removing larger metal particles in the carbonized product by using 1mol/L hydrochloric acid, washing for a plurality of times by using pure water, and drying to obtain the Fe and N doped carbon-based material catalyst (marked as Fe-N-C).
Example 2
Referring to fig. 2, this embodiment is a second embodiment of the present invention, and provides a carbon-based oxygen reduction catalyst, which is prepared by the following steps:
s1: weighing 1g of carbon nano tube and 1.5g of nickel acetylacetonate by using a high-temperature high-pressure gas-phase impregnation method, placing the carbon nano tube and the nickel acetylacetonate in a high-pressure hydrothermal reaction kettle, and impregnating for 4 hours at the temperature of 240 ℃ and under the pressure of 3MPa to obtain a carbon-based material attached with the nickel acetylacetonate;
s2: soaking the carbon-based material attached with the nickel acetylacetonate in an ammonia water solution with the concentration of 25% for 8 hours, and drying at the temperature of 90 ℃ for 10 hours to obtain the carbon-based material attached with the amino nickel coordination compound;
s3: and transferring the dried sample into a porcelain boat, placing the porcelain boat in a tubular furnace, carbonizing the porcelain boat at high temperature for 60min under the argon atmosphere of 900 ℃, naturally cooling to room temperature, removing larger metal particles in a carbonized product by hydrochloric acid, washing the carbonized product for a plurality of times by pure water, and drying to obtain the Ni-N doped carbon-based material catalyst (marked as Ni-N-C).
In this example, the experimental result is shown in fig. 2 by performing an X-ray photoelectron spectrum of the N element in the prepared Ni, N-doped carbon-based material catalyst.
Example 3
This example is a third example of the present invention, and provides a carbon-based oxygen reduction catalyst prepared by the following method:
s1: weighing 1g of commercial carbon black, 1g of cobalt acetylacetonate and 1g of iron acetylacetonate, placing the commercial carbon black, the cobalt acetylacetonate and the 1g of iron acetylacetonate in a closed container by using a high-temperature high-pressure gas-phase impregnation method, and impregnating for 6 hours at the set temperature of 185 ℃ and the pressure of 2MPa to obtain a carbon-based material attached with the cobalt acetylacetonate and the iron acetylacetonate;
s2: and soaking the carbon-based material attached with the cobalt acetylacetonate and the iron acetylacetonate in 28% ammonia water solution for 10 hours, and then drying the carbon-based material at the temperature of 100 ℃ for 20 hours to obtain the carbon-based material attached with the amino cobalt/iron coordination compound.
S3: and drying the carbon-based material attached with the amino cobalt/iron coordination compound, transferring the dried carbon-based material attached with the amino cobalt/iron coordination compound into a porcelain boat, placing the porcelain boat into a tube furnace, and carbonizing the porcelain boat at a high temperature of 1000 ℃ for 60min under the argon atmosphere. Naturally cooling to room temperature, removing larger metal particles by using sulfuric acid, washing for a plurality of times by using ultrapure water, and drying to obtain the Co, fe and N doped carbon-based material catalyst (marked as Co/Fe-N-C).
Test examples
The carbon-based oxygen reduction catalysts prepared in examples 1 to 3 were subjected to a three-electrode system oxygen reduction performance test, and electrochemical performance was tested in a 0.1mol/l koh solution, and the test results are shown in fig. 3:
the results of the above tests show that Co/Fe-N-C has the best catalytic performance and is comparable to commercial Pt/C performance, followed by Ni-N-C, again Fe-N-C.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (10)
1. A carbon-based oxygen reduction catalyst characterized by: the carbon-based oxygen reduction catalyst is prepared by taking a carbon-based carrier as a carbon precursor, acetylacetone metal as a non-noble metal precursor and ammonia water as a ligand displacer.
2. A preparation method of a carbon-based oxygen reduction catalyst is characterized by comprising the following steps:
s1: attaching acetylacetone metal to the surface of a carbon-based carrier by a gas-phase impregnation method to obtain a carbon-based material attached with the acetylacetone metal;
s2: replacing the ligand of the carbon-based material attached with the acetylacetone metal by a liquid phase replacement method by using ammonia water, and drying to obtain the carbon-based material attached with the metal coordination compound of the amino group;
s3: the carbon-based oxygen reduction catalyst is obtained by subjecting the carbon-based material to high-temperature calcination to which the amino complex is attached.
3. The method of claim 2, wherein the carbon-based oxygen reduction catalyst comprises: the conditions of the gas phase impregnation method are high temperature and high pressure.
4. A method of preparing a carbon-based oxygen reduction catalyst according to claim 3, wherein: the conditions of high temperature and high pressure are that the temperature is 150-250 ℃, the pressure is 0-3 MPa, and the processing time is 1-12 h.
5. The method of claim 2, wherein the carbon-based oxygen reduction catalyst comprises: the acetylacetone metal in the S1 is any one or combination of iron acetylacetonate, cobalt acetylacetonate and nickel acetylacetonate, and the carbon-based carrier in the S1 is any one of organic carbon or inorganic carbon.
6. The method of claim 2, wherein the carbon-based oxygen reduction catalyst is prepared by: the concentration of ammonia water in S2 is 25-28%, the replacement time is 0.5-10 h, the drying temperature is 60-100 ℃, and the drying time is 1-24 h.
7. The method of claim 2, wherein the carbon-based oxygen reduction catalyst is prepared by: the high-temperature calcination temperature in the S3 is 300-1100 ℃, and the high-temperature calcination time is 0.2-3 h.
8. The method of claim 2, wherein the carbon-based oxygen reduction catalyst is prepared by: the S3 further comprises: after high-temperature calcination, removing larger metal particles in the carbonized product by acid liquor washing, washing for a plurality of times by ultrapure water, and drying to obtain the carbon-based oxygen reduction catalyst.
9. Use of the carbon-based oxygen reduction catalyst according to claim 1 or the carbon-based oxygen reduction catalyst prepared by the method of any one of claims 2 to 8 in a proton exchange membrane fuel cell.
10. Use of the carbon-based oxygen reduction catalyst according to claim 1 or the carbon-based oxygen reduction catalyst prepared by the method for preparing the oxygen reduction catalyst according to any one of claims 2 to 8 as an oxygen reduction catalyst material for a fuel cell or a metal-air battery.
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