CN114725409A - Platinum-nickel nanocrystalline modified carbon-based catalyst and gram-grade low-pressure preparation method and application thereof - Google Patents
Platinum-nickel nanocrystalline modified carbon-based catalyst and gram-grade low-pressure preparation method and application thereof Download PDFInfo
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- 150000001721 carbon Chemical class 0.000 title claims abstract description 50
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 100
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- 229910052697 platinum Inorganic materials 0.000 claims abstract description 37
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- 229910002844 PtNi Inorganic materials 0.000 claims description 55
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 17
- 239000005711 Benzoic acid Substances 0.000 claims description 16
- 235000010233 benzoic acid Nutrition 0.000 claims description 16
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 13
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 13
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- 239000002245 particle Substances 0.000 claims description 8
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- 235000019445 benzyl alcohol Nutrition 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 34
- 239000001301 oxygen Substances 0.000 abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 33
- 238000006722 reduction reaction Methods 0.000 abstract description 32
- 238000000034 method Methods 0.000 abstract description 9
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a platinum-nickel nanocrystalline modified carbon-based catalyst, a gram-grade low-pressure preparation method and application thereof. The gram-scale low-pressure preparation method comprises the following steps: and reacting a mixed reaction system containing a platinum precursor, a nickel precursor, carbon black, a stabilizer, a structure directing agent and a solvent at the temperature of 130-210 ℃ under normal pressure for 12 hours to obtain the platinum-nickel nanocrystalline modified carbon-based catalyst. The oxygen reduction reaction performance of the platinum-nickel nanocrystalline modified carbon-based catalyst prepared by the method is remarkably improved, and meanwhile, the platinum-nickel nanocrystalline modified carbon-based catalyst can be synthesized under normal pressure, has the advantages of low platinum content, excellent oxygen reduction performance, high stability, gram-scale production and preparation and the like, can greatly reduce the production cost, and has very wide industrial application prospects.
Description
Technical Field
The invention belongs to the technical field of material and energy catalysis, and particularly relates to a platinum-nickel nanocrystalline modified carbon-based catalyst, a gram-level low-pressure preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are clean energy sources with great potential, but their performance is greatly limited by the Oxygen Reduction Reaction (ORR). Fuel cells have been considered as the most efficient and clean energy conversion device, and fuel and oxygen react without combustion through a mild electrochemical process, and can directly convert the huge chemical energy contained in hydrogen or hydrocarbons into clean, stable and sustainable electric energy through an electrochemical pathway at near room temperature, thus being considered as one of the most promising solutions to meet the growing world energy demand. However, in practical applications, low temperature fuel cells do not exhibit such efficiency, primarily due to the slow oxygen reduction reaction at the cathode. In a typical hydrogen fuel cell, hydrogen is oxidized at the positive electrode and oxygen is reduced at the negative electrode, and the oxygen reduction reaction proceeds more slowly than the hydrogen oxidation reaction from a kinetic point of view, and thus becomes an important factor for restricting the development of the fuel cell. Among many catalysts, the noble metal platinum-based catalyst has extremely high activity in ORR reaction and wide application prospect. The widespread use of platinum-based catalysts in fuel cells has some drawbacks. The main reasons are that the supply of platinum is very limited, the price is high, the batch preparation is difficult, and the method is not suitable for large-scale industrial application; therefore, the reasonable design of the platinum-based catalyst with low platinum loading and high stability and the preparation method of the product capable of being synthesized in a large scale have important significance in practical application.
Through doping of different metals, the electronic structure of the noble metal platinum is changed, so that the noble metal platinum has better oxygen reduction reaction performance. And the platinum nickel nanocrystalline particles are loaded on the high-activity carbon carrier, so that the content of noble metal platinum is reduced, and the electron transmission rate in the reaction process is improved. The synthesis method is simple and convenient, can improve the yield of the catalyst to gram level under normal pressure under the action of the stabilizer, and improves the performance of oxygen reduction reaction under low platinum content. The technology can improve the yield of the catalyst from milligram level to gram level, and the low platinum content greatly reduces the production cost of the platinum-based catalyst, thereby providing a certain foundation for large-scale commercial application of fuel cells.
Disclosure of Invention
The invention mainly aims to provide a platinum-nickel nanocrystalline modified carbon-based catalyst, a gram-level low-pressure preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a gram-grade low-pressure preparation method of a platinum-nickel nanocrystalline modified carbon-based catalyst, which comprises the following steps: and reacting a mixed reaction system containing a platinum precursor, a nickel precursor, carbon black, a stabilizer, a structure directing agent and a solvent at the temperature of 130-210 ℃ under normal pressure for 12 hours to obtain the platinum-nickel nanocrystalline modified carbon-based catalyst.
The embodiment of the invention also provides the platinum-nickel nanocrystalline modified carbon-based catalyst prepared by the gram-scale low-pressure preparation method, wherein the particle size of PtNi particles in the platinum-nickel nanocrystalline modified carbon-based catalyst is 3-4 nm; the Pt content in the platinum-nickel nanocrystalline modified carbon-based catalyst is 3.00-3.36 wt%.
The embodiment of the invention also provides application of the platinum-nickel nanocrystalline modified carbon-based catalyst in preparation of a fuel cell.
Compared with the prior art, the invention has the beneficial effects that:
(1) under the action of a structure directing agent and a stabilizing agent, a platinum-nickel precursor is loaded on a carbon-based carrier, the particle size of PtNi particles in the synthesized platinum-nickel nanocrystalline modified carbon-based catalyst is 3-4nm, the platinum content is only 3.00-3.36 wt%, and the specific activity in the oxygen reduction reaction of the platinum-nickel nanocrystalline modified carbon-based catalyst is respectively 9.28 times and 6.47 times of that of a commercial Pt/C-5% (Pt content is 5%) and that of a commercial Pt/C-20% (Pt content is 20%);
(2) the platinum-nickel nanocrystalline modified carbon-based catalyst can be carried out under normal pressure, has the advantages of low platinum content, excellent oxygen reduction performance, high stability, gram-scale production and preparation and the like, can greatly reduce the production cost, and has very wide industrial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of PtNi/C catalyst modified with Pt-Ni nanocrystals in this example 1;
FIG. 2 is a transmission electron micrograph of PtNi/C catalyst modified with Pt-Ni nanocrystals in this example 1;
FIG. 3 is an XRD spectrum of PtNi/C catalyst modified by Pt-Ni nanocrystals in this example 1;
FIG. 4 is a schematic diagram of a gram-size synthesis preparation apparatus in this example 1;
FIG. 5 is a graph showing the results of performance tests of the PtNi/C catalysts synthesized in examples 1 to 6 of the present invention by oxygen reduction reaction in an alkaline solution (0.1M potassium hydroxide);
FIG. 6 is a graph showing the results of performance tests of the PtNi/C catalysts synthesized at different Pt/Ni ratios in alkaline solution (0.1M KOH) according to examples 7 to 11 of the present invention;
FIG. 7 is a graph showing the performance of oxygen reduction reactions of PtNi/C-200 ℃ to Pt: Ni of 1: 2 in example 10 of the present invention, and commercial Pt/C-5% and commercial Pt/C-20% in comparative example 1;
FIG. 8 is a transmission electron micrograph of a catalyst prepared according to comparative example 2 of the present invention;
FIG. 9 is a transmission electron micrograph of a catalyst prepared according to comparative example 3 of the present invention;
FIG. 10 is a transmission electron micrograph of a catalyst prepared according to comparative example 4 of the present invention;
FIG. 11 is a graph showing the performance test of the oxygen reduction reaction of the catalysts prepared in comparative examples 2 to 4 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a large amount of practice, and discloses a gram-scale low-pressure preparation method of a platinum-nickel nanocrystal modified carbon-based catalyst to solve the problem of high preparation cost of the existing commercial platinum-based catalyst. The synthesis method can realize gram-level preparation of the catalyst at normal temperature, and the carbon base is modified by the platinum-nickel nanocrystalline with low platinum loading capacity, so that excellent catalytic performance is achieved. The preparation method is simple and easy to implement, the size of the synthesized nano-crystal is 3-4nm, the nano-crystal is uniformly dispersed on the carbon-based carrier, and the nano-crystal has extremely high stability.
The noble metal platinum and the nickel of the subgroup element form alloy, so that the electronic structure of the noble metal platinum is changed, and the catalytic performance of the noble metal platinum in the oxygen reduction reaction process is improved; the nickel and the platinum form an alloy and are loaded on the carbon carrier, so that the formed alloy is more uniformly distributed, the utilization rate of platinum atoms is improved, the content of noble metal platinum in the oxygen reduction catalyst is effectively reduced, and the cost of industrial application is reduced. Under the action of benzoic acid and hexadecyl trimethyl ammonium bromide, stable platinum-nickel nano crystals can be formed under normal pressure, and the platinum-nickel nano crystals are small in size and not easy to aggregate. By the synthesis method, the yield of the catalyst is improved from milligram level to gram level, and the synthesis method has important significance for further commercial application of fuel cells.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Specifically, as one aspect of the technical scheme of the invention, the gram-scale low-pressure preparation method of the platinum-nickel nanocrystalline modified carbon-based catalyst comprises the following steps: and reacting a mixed reaction system containing a platinum precursor, a nickel precursor, carbon black, a stabilizer, a structure directing agent and a solvent at the temperature of 130-210 ℃ under normal pressure for 12 hours to obtain the platinum-nickel nanocrystalline modified carbon-based catalyst.
In some preferred embodiments, the gram-scale low pressure production process comprises: dispersing a platinum precursor, a nickel precursor, carbon black, a stabilizer and a structure directing agent in a solvent to form the mixed reaction system.
In some preferred embodiments, the platinum precursor includes platinum acetylacetonate and/or potassium tetrachloroplatinate, and is not limited thereto.
In some preferred embodiments, the nickel precursor includes nickel acetylacetonate and/or nickel chloride, and is not limited thereto.
In some preferred embodiments, the stabilizer includes benzoic acid, and is not limited thereto.
In some preferred embodiments, the structure directing agent comprises cetyltrimethylammonium bromide, wherein the cetyltrimethylammonium bromide acts to stabilize the PtNi nanocrystals and control their particle size, forming PtNi nanoparticles of smaller size.
In some preferred embodiments, the carbon black includes any one or a combination of two or more of Vulcan XC-72, ketjen black, and acetylene black, and is not limited thereto.
In some preferred embodiments, the solvent includes benzyl alcohol, and is not limited thereto.
In some preferred embodiments, the mass ratio of the platinum precursor to the nickel precursor is 3: 1 to 1: 3.
In some preferred embodiments, the mass ratio of carbon black to platinum precursor is 11.25: 1.
In some preferred embodiments, the mass ratio of the stabilizer to the platinum precursor is 6.25: 1.
In some preferred embodiments, the mass ratio of the structure directing agent to the platinum precursor is 10.00: 1.
In some preferred embodiments, the gram-scale low pressure production process further comprises: after the reaction is finished, washing, centrifuging and drying the obtained product.
Further, the obtained product is washed and centrifuged by ethanol and acetone.
In some more specific embodiments, the gram-scale low-pressure preparation method of the platinum-nickel nanocrystal modified carbon-based catalyst comprises the following steps:
(1) weighing platinum precursors and nickel precursors in different proportions, and stirring the precursors into a uniform solution at room temperature under the action of a stabilizer and a structure directing agent;
(2) placing the solution in the step (1) in an oil bath device, setting the reaction temperature, and preparing a sample under normal pressure;
(3) adding ethanol and acetone into the sample synthesized in the step (2) to clean and centrifuge the sample;
(4) and (4) placing the sample obtained by centrifugation in the step (3) into a vacuum drying oven for drying treatment to obtain the platinum-nickel nanocrystalline modified carbon-based catalyst.
Further, in the step (2), the reaction temperature is: any one of 130 ℃ or 150 ℃ or 170 ℃ or 190 ℃ or 200 ℃ or 210 ℃.
Another aspect of the embodiment of the invention also provides a platinum-nickel nanocrystal modified carbon-based catalyst prepared by the gram-scale low-pressure preparation method, wherein the particle size of PtNi particles in the platinum-nickel nanocrystal modified carbon-based catalyst is 3-4 nm; the Pt content in the platinum-nickel nanocrystalline modified carbon-based catalyst is 3.00-3.36 wt%, and preferably 3.04 wt%.
The embodiment of the invention also provides application of the platinum-nickel nanocrystalline modified carbon-based catalyst in preparation of a fuel cell.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) 90mg of carbon black (Vulcan XC-72), 10.28mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of a solvent and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12h at 130 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifuging to separate a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12 hours to obtain the Pt-Ni nanocrystalline modified carbon-based catalyst PtNi/C (recording as the synthesis PtNi/C-130 ℃). The PtNi/C catalyst synthesized at the temperature has better catalytic performance on the oxygen reduction reaction. The yield of the PtNi/C catalyst in this example was 1.15 g.
FIG. 1 is a scanning electron micrograph of a Pt/Ni nanocrystal-modified carbon-based catalyst PtNi/C in this example; FIG. 2 is a transmission electron micrograph of a Pt/Ni nanocrystal-modified carbon-based catalyst PtNi/C in this example; FIG. 3 is an XRD spectrum of PtNi/C catalyst modified by Pt-Ni nanocrystals in this example; FIG. 4 is a schematic view of a gram-scale synthesis preparation apparatus of this example.
Example 2
(1) 90mg of carbon black (Vulcan XC-72), 10.28mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of a solvent and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12h at 150 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifugally separating out a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12 hours to obtain the Pt-Ni nanocrystalline modified carbon-based catalyst PtNi/C (recorded as synthesizing PtNi/C-150 ℃). The PtNi/C catalyst synthesized at the temperature has better catalytic performance on the oxygen reduction reaction.
Example 3
(1) 90mg of carbon black (Vulcan XC-72), 10.28mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of a solvent and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12h at 170 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifugally separating out a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12 hours to obtain the Pt-Ni nanocrystalline modified carbon-based catalyst PtNi/C (recorded as synthesizing PtNi/C-170 ℃). The PtNi/C catalyst synthesized at the temperature has better catalytic performance on the oxygen reduction reaction.
Example 4
(1) 90mg of carbon black (Vulcan XC-72), 10.28mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of a solvent and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12h at 190 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifugally separating out a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12 hours to obtain the Pt-Ni nanocrystalline modified carbon-based catalyst PtNi/C (recorded as synthesizing PtNi/C-190 ℃). The PtNi/C catalyst synthesized at the temperature has better catalytic performance on the oxygen reduction reaction.
Example 5
(1) 90mg of carbon black (Vulcan XC-72), 10.28mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of a solvent and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12h at 200 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifugally separating out a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12 hours to obtain the PtNi/C catalyst (recorded as synthesizing PtNi/C-200 ℃) modified carbon-based catalyst with excellent catalytic performance on the oxygen reduction reaction at the temperature.
Example 6
(1) 90mg of carbon black (Vulcan XC-72), 10.28mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of a solvent and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12h at 210 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifugally separating out a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12 hours to obtain the PtNi/C catalyst (recorded as synthesizing PtNi/C-210 ℃) modified carbon-based catalyst with excellent catalytic performance on the oxygen reduction reaction at the temperature.
FIG. 5 shows the results of performance tests of the PtNi/C catalysts synthesized in examples 1 to 6 of the present invention by oxygen reduction in an alkaline solution (0.1M potassium hydroxide) at different temperatures. By comparison, it was found that the test results of the catalytic oxygen reduction reaction performance were better as the temperature increased when the sample was synthesized when the temperature was increased from 130 ℃ to 200 ℃, and that the temperature-to-oxygen reduction reaction performance was slightly inferior to that of the PtNi/C catalyst synthesized at 200 ℃ when the temperature was increased to 210 ℃, but still had excellent catalyst activity for the oxygen reduction reaction. Therefore, the PtNi/C catalyst synthesized at 200 ℃ is the optimum temperature for synthesizing the sample.
The PtNi/C catalyst synthesized at different temperatures in the invention shows excellent catalytic performance of oxygen reduction reaction in an acid solution (0.1M perchloric acid). And the synthesized catalyst shows excellent catalytic activity for oxygen reduction reaction under the conditions of different temperatures (130 ℃, or 150 ℃, or 170 ℃, or 190 ℃, or 200 ℃ or 210 ℃) which are researched.
Example 7
(1) 90mg of carbon black (Vulcan XC-72), 1.742mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of benzyl alcohol and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12h at 200 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifuging to separate a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12h to obtain the Pt-Ni nanocrystalline modified carbon-based catalyst PtNi/C (recorded as synthesizing PtNi/C-200 ℃ -Pt: Ni ═ 3: 1). The composition of the platinum-nickel nanocrystal modified carbon-based catalyst PtNi/C is shown in Table 1.
Example 8
(1) 90mg of carbon black (Vulcan XC-72), 2.613mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of benzyl alcohol and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12 hours at 200 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifugally separating out a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12h to obtain the Pt-Ni nanocrystalline modified carbon-based catalyst PtNi/C (recorded as synthesizing PtNi/C-200 ℃ -Pt: Ni ═ 2: 1). The composition of the platinum-nickel nanocrystal modified carbon-based catalyst PtNi/C is shown in Table 1.
Example 9
(1) 90mg of carbon black (Vulcan XC-72), 5.203mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of benzyl alcohol and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12h at 200 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifuging to separate a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12 hours to obtain the Pt-Ni nanocrystalline modified carbon-based catalyst PtNi/C (recording as synthesis PtNi/C-200 ℃ -Pt: Ni as 1: 1). The composition of the platinum-nickel nanocrystal modified carbon-based catalyst PtNi/C is shown in Table 1.
Example 10
(1) 90mg of carbon black (Vulcan XC-72), 10.451mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of benzyl alcohol and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12h at 200 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifugally separating out a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12h to obtain the Pt-Ni nanocrystalline modified carbon-based catalyst PtNi/C (recorded as synthesizing PtNi/C-200 ℃ -Pt: Ni ═ 1: 2). The composition of the platinum-nickel nanocrystal modified carbon-based catalyst PtNi/C is shown in Table 1.
Example 11
(1) 90mg of carbon black (Vulcan XC-72), 15.677mg of nickel acetylacetonate, 80mg of cetyltrimethylammonium bromide, 50mg of benzoic acid and 8mg of platinum acetylacetonate were dissolved in 5mL of benzyl alcohol and stirred until the solution became homogeneous. Then transferring the solution into an oil bath device, and reacting for 12h at 200 ℃;
(2) washing the product synthesized in the step (1) with ethanol and acetone, and then centrifugally separating out a solid product;
(3) and (3) drying the sample synthesized in the step (2) in a drying oven for 12h to obtain the Pt-Ni nanocrystalline modified carbon-based catalyst PtNi/C (recorded as synthesizing PtNi/C-200 ℃ -Pt: Ni ═ 1: 3). The composition of the platinum-nickel nanocrystal modified carbon-based catalyst PtNi/C is shown in Table 1.
TABLE 1 compositions of platinum-Nickel nanocrystalline modified carbon-based catalysts prepared in examples 7-11
FIG. 6 shows the results of performance tests of the PtNi/C catalysts synthesized in examples 7 to 11 according to the present invention by oxygen reduction reaction in alkaline solution (0.1M potassium hydroxide). By comparison, it was found that the test results of the catalytic oxygen reduction performance were better as the platinum-nickel ratio increased when the platinum-nickel ratio was increased from 3: 1 to 1: 2, and that the platinum-nickel ratio vs. oxygen reduction performance was slightly inferior to that of the PtNi/C catalyst synthesized when the platinum-nickel ratio was increased to 1: 3. Therefore, the synthesized PtNi/C catalyst with the platinum-nickel ratio of 1: 2 is the optimal platinum-nickel ratio of the synthesized sample.
Comparative example 1
Carrying out oxygen reduction reaction performance test by adopting commercial Pt/C-5% and commercial Pt/C-20%;
FIG. 7 is a graph showing the performance of oxygen reduction reactions of PtNi/C-200 ℃ to Pt: Ni of 1: 2 in example 10 of the present invention, commercial Pt/C-5% in comparative example 1, and commercial Pt/C-20%.
Comparative example 2
The procedure is as in example 10, except that no stabilizer, benzoic acid, is used; fig. 8 is a transmission electron micrograph of the catalyst prepared in this comparative example 2.
Comparative example 3
The process is the same as example 10 except that the structure directing agent cetyl trimethylammonium bromide is not used; fig. 9 is a transmission electron micrograph of the catalyst prepared in this comparative example 3.
Comparative example 4
The method is the same as example 10, except that a stabilizer, benzoic acid, and a structure directing agent, cetyltrimethylammonium bromide, are not used; FIG. 10 is a transmission electron micrograph of the catalyst prepared in this comparative example 4; FIG. 11 is a graph showing oxygen reduction reaction performance test of the catalysts prepared in comparative examples 2 to 4.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.
Claims (10)
1. A gram-level low-pressure preparation method of a platinum-nickel nanocrystalline modified carbon-based catalyst is characterized by comprising the following steps: and reacting a mixed reaction system containing a platinum precursor, a nickel precursor, carbon black, a stabilizer, a structure directing agent and a solvent at the temperature of 130-210 ℃ under normal pressure for 12 hours to obtain the platinum-nickel nanocrystalline modified carbon-based catalyst.
2. The gram-scale low pressure production process according to claim 1, characterized by comprising: dispersing a platinum precursor, a nickel precursor, carbon black, a stabilizer and a structure directing agent in a solvent to form the mixed reaction system.
3. The gram-scale low pressure production process of claim 1 wherein: the platinum precursor includes platinum acetylacetonate and/or potassium tetrachloroplatinate.
4. The gram-scale low pressure production process of claim 1 wherein: the nickel precursor comprises nickel acetylacetonate and/or nickel chloride.
5. The gram-scale low pressure production process of claim 1 wherein: the stabilizer comprises benzoic acid;
and/or, the structure directing agent comprises cetyltrimethylammonium bromide.
6. The gram-scale low pressure production process of claim 1 wherein: the carbon black comprises any one or the combination of more than two of Vulcan XC-72, Ketjen black and acetylene black;
and/or, the solvent comprises benzyl alcohol.
7. The gram-scale low pressure production process of claim 1 wherein: the mass ratio of the platinum precursor to the nickel precursor is 3: 1-1: 3;
and/or the mass ratio of the carbon black to the platinum precursor is 11.25: 1;
and/or the mass ratio of the stabilizer to the platinum precursor is 6.25: 1;
and/or the mass ratio of the structure directing agent to the platinum precursor is 10.00: 1.
8. The gram-scale low pressure production process of claim 1 further comprising: after the reaction is finished, washing, centrifuging and drying the obtained product; preferably, the obtained product is washed and centrifuged by using ethanol and acetone.
9. The gram-scale low-pressure preparation method of any one of claims 1 to 8, wherein the Pt/Ni/nanocrystalline modified carbon-based catalyst has a PtNi particle size of 3 to 4 nm; the Pt content in the platinum-nickel nanocrystalline modified carbon-based catalyst is 3.00-3.36 wt%.
10. Use of the platinum nickel nanocrystalline modified carbon based catalyst according to claim 9 for the preparation of a fuel cell.
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