CN118117105A - High specific surface area porous carbon-based platinum catalyst and preparation method and application thereof - Google Patents
High specific surface area porous carbon-based platinum catalyst and preparation method and application thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 53
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000010453 quartz Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 7
- 239000011592 zinc chloride Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 150000003057 platinum Chemical class 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- -1 transition metal salt Chemical class 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 27
- 230000009467 reduction Effects 0.000 claims description 11
- 239000000446 fuel Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 4
- 229910001260 Pt alloy Inorganic materials 0.000 abstract description 3
- 230000010757 Reduction Activity Effects 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 30
- 239000000956 alloy Substances 0.000 description 30
- 238000006722 reduction reaction Methods 0.000 description 20
- 229910002837 PtCo Inorganic materials 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000010431 corundum Substances 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 10
- 229910052573 porcelain Inorganic materials 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
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- 239000003575 carbonaceous material Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
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- 238000005054 agglomeration Methods 0.000 description 4
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- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- IEKWPPTXWFKANS-UHFFFAOYSA-K trichlorocobalt Chemical group Cl[Co](Cl)Cl IEKWPPTXWFKANS-UHFFFAOYSA-K 0.000 description 3
- 102000020897 Formins Human genes 0.000 description 2
- 108091022623 Formins Proteins 0.000 description 2
- 229910002844 PtNi Inorganic materials 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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Abstract
A porous carbon-based platinum catalyst with high specific surface area and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing 2-aminobenzimidazole and zinc chloride, placing the mixture in a sealed quartz tube, placing the quartz tube in a muffle furnace, and carrying out molten salt reaction under high temperature conditions; after the reaction is finished and cooled to room temperature, grinding the obtained solid, washing with water and ethanol, and drying in vacuum; then, carrying out high-temperature pyrolysis treatment on the dried material in an inert atmosphere to obtain nitrogen-doped porous carbon; dispersing nitrogen doped porous carbon in an aqueous solution, adding precursors of platinum salt and transition metal salt, stirring, distilling under reduced pressure, drying, transferring to a tube furnace, and calcining at high temperature to obtain the porous carbon-based platinum catalyst with high specific surface area. The platinum alloy in the catalyst has good crystallinity, small particle size, uniform distribution and high atom utilization rate; not only is the platinum loading low in this catalyst, but the electrocatalytic oxygen reduction activity is superior to the commercial 70% pt/C catalyst.
Description
Technical Field
The invention relates to the field of inorganic materials and energy catalysis, in particular to a porous carbon-based platinum catalyst with high specific surface area, a preparation method and application thereof.
Background
Under the background of carbon neutralization and carbon reaching peak double carbon, developing efficient green energy storage and conversion technology becomes a main research direction of vast scientific researchers. Proton Exchange Membrane Fuel Cells (PEMFCs) exhibit good application prospects as an efficient clean energy conversion technology. Oxygen Reduction Reaction (ORR) is an important half-reaction in PEMFC, directly affecting the performance of the battery. At present, the catalyst with the best activity and stability is a Pt catalyst, but the price of Pt greatly increases the cost of the catalyst and the battery. The method reduces the platinum carrying capacity on the premise of ensuring high activity, and has great significance for promoting the commercial application of the platinum-based catalyst.
Porous carbon is a material with high surface area and chemical stability, and is a good carrier for platinum nanoparticles. Porous carbon has the following advantages over other carbon supports: 1. the sources are more, the preparation method is simple and convenient, and the cost is low: 2. the conductivity is good: the carbon material has good conductivity, and is beneficial to electron conduction in the electrochemical reaction process; 3. abundant pore structure: the high surface area of the porous carbon material is beneficial to exposing more catalytic active sites, promoting the contact of the catalytic active sites with electrolyte and improving the catalytic activity; at present, a plurality of preparation methods are reported for preparing carbon-supported platinum-based composite catalysts, such as a sol-gel method, a metal-organic framework limiting co-reduction method and the like. However, the preparation methods are generally complicated, are not easy to prepare in large quantities, and limit practical application. For example: the sol-gel method has the problems of harsh production conditions, low yield and the like, and the metal-organic framework limiting co-reduction method has the problems of complicated operation steps, high production cost and the like.
Disclosure of Invention
The nitrogen-doped porous carbon material has good application prospect in the field of electrocatalytic oxygen reduction, and hetero atoms are introduced into the carbon material, so that not only can the electron cloud density of a carbon skeleton be regulated and controlled, but also the lower electronegativity of the nitrogen-doped porous carbon material can be used for anchoring platinum nano particles, thereby reducing the agglomeration of platinum and having good promotion effect on improving the performance of the catalyst. The nitrogen doped porous carbon is constructed, and the carbon supported platinum catalyst is prepared by taking the nitrogen doped porous carbon as a carrier, so that breakthrough of catalytic performance is expected to be realized. Based on the above, the invention provides a porous carbon-based platinum catalyst with high specific surface area, and a preparation method and application thereof, and aims to improve the catalytic activity of the catalyst, reduce the Pt load and reduce the preparation cost.
In order to achieve the above purpose, the invention provides a preparation method of a porous carbon-based platinum catalyst with high specific surface area, which utilizes a molten salt method to prepare a nitrogen-doped porous carbon material, avoids metal agglomeration through the confinement effect of a porous structure and the anchoring effect of hetero atoms, improves the catalytic activity and reduces the preparation cost. The preparation method comprises the following steps:
(1) Mixing 2-aminobenzimidazole and zinc chloride, placing the mixture in a sealed quartz tube, placing the quartz tube in a muffle furnace, and carrying out molten salt reaction under high temperature conditions;
(2) After the reaction in the step (1) is finished and cooled to room temperature, grinding the obtained solid, washing with water and ethanol, and drying in vacuum; then, carrying out high-temperature pyrolysis treatment on the dried material in an inert atmosphere to obtain nitrogen-doped porous carbon;
(3) Dispersing the obtained nitrogen doped porous carbon in an aqueous solution, adding precursors of platinum salt and transition metal salt, stirring, distilling under reduced pressure, drying, and transferring to a tube furnace for high-temperature calcination to obtain the porous carbon-based platinum catalyst with high specific surface area.
As a further preferable technical scheme of the invention, in the step (1), the mass ratio of the 2-aminobenzimidazole to the zinc chloride is 1:5.
As a further preferable technical scheme of the invention, in the step (1), the temperature of the molten salt reaction is 600-900 ℃ and the reaction time is 40 hours.
As a further preferable embodiment of the present invention, in the step (1), the 2-aminobenzimidazole and zinc chloride are transferred to a quartz tube after being sufficiently ground in a glove box.
As a further preferable technical scheme of the invention, in the step (2), the high-temperature pyrolysis temperature is 800-1000 ℃ and the time is 2-5h.
In a further preferable embodiment of the present invention, in the step (3), the platinum salt is chloroplatinic acid, and the transition metal salt is one or more of cobalt chloride, copper chloride, ferric chloride and nickel chloride.
As a further preferable embodiment of the present invention, in the step (3), the atmosphere of high-temperature calcination is 5% H 2/Ar mixed gas.
As a further preferable technical scheme of the invention, in the step (3), the high-temperature calcination temperature is 600-1000 ℃ and the time is 2 hours.
According to another aspect of the invention, the invention also provides a porous carbon-based platinum catalyst with high specific surface area, which is prepared by the method.
According to another aspect of the invention, the invention also provides the use of a high specific surface area porous carbon-based platinum catalyst as an electrocatalytic oxygen reduction electrocatalyst in a fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
1) The porous carbon prepared by the method has high specific surface area and nitrogen content, and the high specific surface area is favorable for exposing more active sites and reaction mass transfer and has good promotion effect on improving the catalytic activity of the catalyst; the high nitrogen content helps anchor the metal atoms, reducing Pt agglomeration;
2) The platinum alloy in the catalyst prepared by the invention has good crystallinity, small particle size, uniform distribution and high atom utilization rate;
3) The gold catalyst prepared by the invention has low platinum carrying capacity and better electrocatalytic oxygen reduction activity than a commercial 70% Pt/C catalyst, wherein the half-wave potential of the PtCo alloy catalyst reaches 0.940V, and the PtCo alloy catalyst is used as a cathode catalyst of a fuel cell, and has the power density of 976mW cm -2.
4) The preparation method provided by the invention has the advantages of high yield, simplicity in operation, low equipment requirement, low cost, easiness in mass preparation and high practical application prospect.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is an X-ray diffraction pattern of the PtCo alloy catalyst of example 1;
FIG. 2 is a graph showing the physical adsorption/desorption curves of nitrogen for the PtCo alloy catalyst of example 1;
FIG. 3 is a transmission electron micrograph of the PtCo alloy catalyst of example 1;
FIG. 4 is a graph showing the polarization of the oxygen reduction reaction of the catalyst samples of examples 1-4 and comparative example 1 in 0.1M HClO 4;
fig. 5 shows the performance of the hydrogen-air fuel cell in which the PtCo alloy is the cathode in example 1.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The method utilizes 2-aminobenzimidazole rich in nitrogen heteroatom as a precursor, and prepares the nitrogen-doped porous carbon with high specific surface area by a molten salt method; and then, compounding porous carbon and platinum salt, calcining at high temperature, and utilizing the anchoring action of nitrogen in the porous carbon and the porous limiting action to limit the migration of platinum atoms and reduce platinum agglomeration, so as to prepare a series of porous carbon-supported platinum alloy composite catalysts which are applied to electrocatalytic oxygen reduction reaction and fuel cells.
In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention will be further described in detail by means of specific examples.
Example 1
The preparation method of the porous carbon-based platinum catalyst with high specific surface area provided by the embodiment comprises the following steps:
(a) The 2-aminobenzimidazole (0.85 mmol) and ZnCl 2 (3.7 mmol) were first ground together in a glove box and then transferred to a quartz tube, which was sealed with a tube sealer.
(B) Then placing the sealed quartz tube into a muffle furnace, heating at 800 ℃ for 40h (the heating rate is 5 ℃ for min -1), and naturally cooling to room temperature; the resulting solid was washed with water and ethanol to remove residual ZnCl 2 and dried in vacuo at 60 ℃. And then, carrying out second heat treatment (1000 ℃ C., 4 hours, and the heating rate is 5 ℃ C., min -1) on the dried material in N 2 atmosphere to obtain the N-doped porous carbon.
(C) Adding 100mg of N-doped porous carbon into 300ml of deionized water, and performing ultrasonic dispersion; subsequently, 87mg of sodium chloroplatinate and 52mg of cobalt chloride were added, stirred for 10 hours, and ultrasonically dispersed for 1 hour; and removing water by a rotary evaporator to obtain a mixture of the supported metal salt.
(D) Transferring the mixture of the loaded metal salt into a corundum porcelain boat, and putting the corundum porcelain boat into a tube furnace. Under the atmosphere of 5% hydrogen/argon gas mixture, the temperature is raised to 900 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 2h, and the mixture is naturally cooled to room temperature, so that the nitrogen-doped porous carbon-supported PtCo alloy composite material (hereinafter referred to as PtCo alloy catalyst) is obtained, namely the porous carbon-based platinum catalyst with high specific surface area.
The following is a structural characterization of the catalyst sample obtained in example 1:
The PtCo alloy catalyst prepared in example 1 was subjected to X-ray diffraction (XRD) test, the generator voltage was 40kV, the generator current was 40mA, and the scanning speed was 6℃min -1. The XRD spectrum line of FIG. 1 shows that the material has obvious diffraction peaks at 24 degrees, 34.7 degrees, 42.1 degrees and 48.3 degrees, and is matched with the signal of a PtCo alloy standard card, thus indicating that the PtCo alloy composite material is successfully prepared. The PtCo alloy catalyst prepared in example 1 was subjected to nitrogen physical adsorption/desorption test, and the pore structure of the material was studied. Based on the adsorption/desorption curve of FIG. 2, the specific surface area of the material is calculated, the specific surface area of the material reaches 2160m 2/g, and the high specific surface area is favorable for exposing more active sites and reaction mass transfer and has good promotion effect on improving the catalytic activity of the catalyst.
Transmission Electron Microscope (TEM) testing was performed on the PtCo alloy catalyst obtained in example 1. A small amount of sample of example 1 was dispersed on a conductive tape for TEM test, and the result is shown in FIG. 3, wherein PtCo alloy nanoparticles in the material are uniformly distributed, and the particle size is about 5 nm. The PtCo alloy particles are small and uniformly distributed, so that more active sites are exposed, and the promotion of catalytic activity is well promoted.
The comparative performance test for the electrocatalytic oxygen reduction reaction of the catalyst sample prepared in example 1 and the existing commercial 70wt.% Pt/C catalyst is as follows:
As shown in FIG. 4, the PtCo alloy catalyst prepared exhibited excellent oxygen reduction catalytic performance in 0.1M HClO 4, with an ultimate current density of 5.8mA cm -2, a half-wave potential of 0.940V, a Pt/C catalyst exceeding 70wt.% of commercial TKK, and other catalysts (TEC 10E70 TPM).
Comparative example 1
As a control experimental group of example 1, the difference is that: the N-doped carbon support was not subjected to a secondary calcination treatment. The method comprises the following steps:
(a) The 2-aminobenzimidazole (0.85 mmol) and ZnCl 2 (3.7 mmol) were first ground together in a glove box and then transferred to a quartz tube, which was sealed with a tube sealer.
(B) And then placing the sealed quartz tube into a muffle furnace, heating at 800 ℃ for 40h (the heating rate is 5 ℃ for min -1), and naturally cooling to room temperature. The resulting solid was washed with water and ethanol to remove residual ZnCl 2 and dried in vacuo at 60 ℃ to give an N-doped porous carbon. And then directly taking the dried material as a carbon carrier without secondary heat treatment.
(C) Adding 100mg of N-doped porous carbon into 300ml of deionized water, and performing ultrasonic dispersion; subsequently, 87mg of sodium chloroplatinate and 52mg of cobalt chloride were added, stirred for 10 hours, and further dispersed by ultrasonic waves for 1 hour. The water was removed by rotary evaporator to give a mixture of supported metal salts.
(D) Transferring the mixture into a corundum porcelain boat, and putting the corundum porcelain boat into a tube furnace. Heating to 900 ℃ at a heating rate of 2 ℃/min under the atmosphere of 5% hydrogen/argon gas mixture, preserving heat for 2h, and naturally cooling to room temperature. Obtaining the nitrogen-doped porous carbon-supported PtCo-2 alloy composite material (hereinafter referred to as PtCo-2 alloy catalyst).
The following are comparative example 1 preparation samples electrocatalytic oxygen reduction reaction performance tests:
As shown in FIG. 4, the limiting current density of the prepared PtCo-2 alloy catalyst in 0.1M HClO 4 reaches 5.8 mA.cm -2, and the half-wave potential reaches 0.917V. Example 1 compared to comparative example 1, the oxygen reduction half-wave potential was increased by 23mV after the carbon support was subjected to secondary calcination. Thus, it can be seen that the second heat treatment of the carbon support makes a great difference in oxygen reduction performance, which has a great influence on the high oxygen reduction performance of the catalyst.
Example 2
The main difference between this embodiment and embodiment 1 is that: the chloride salt cobalt chloride was replaced with copper chloride. The method comprises the following specific steps:
(a) The procedure was the same as in example 1.
(B) The procedure was the same as in example 1.
(C) Adding 100mg of N-doped porous carbon into 300ml of deionized water, and performing ultrasonic dispersion; subsequently, 90mg of sodium chloroplatinate and 59mg of copper chloride were added, stirred for 10 hours, and further dispersed by ultrasonic sound for 1 hour. The water was removed by rotary evaporator to give a mixture of supported metal salts.
(D) Transferring the mixture into a corundum porcelain boat, and putting the corundum porcelain boat into a tube furnace. Under the atmosphere of 5% hydrogen/argon gas mixture, the temperature is raised to 850 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 2 hours, and the mixture is naturally cooled to the room temperature. And obtaining the nitrogen-doped porous carbon-supported PtCu alloy composite material (hereinafter referred to as PtCu alloy catalyst).
The following are the electrocatalytic oxygen reduction reaction performance tests for the samples prepared in example 2:
As shown in FIG. 4, the PtCu alloy catalyst prepared shows good oxygen reduction catalytic performance in 0.1M HClO 4, the limiting current density reaches 5.8mA cm -2, and the half-wave potential reaches 0.910V.
Example 3
The main difference between this embodiment and embodiment 1 is that: the chloride salt cobalt chloride was replaced with nickel chloride. The method comprises the following specific steps:
(a) The procedure was the same as in example 1.
(B) The procedure was the same as in example 1.
(C) Adding 100mg of N-doped porous carbon into 300ml of deionized water, and performing ultrasonic dispersion; subsequently, 88mg of sodium chloroplatinate and 55mg of nickel chloride were added, stirred for 10 hours, and further dispersed by ultrasonic waves for 1 hour. The water was removed by rotary evaporator to give a mixture of supported metal salts.
(D) Transferring the mixture into a corundum porcelain boat, and putting the corundum porcelain boat into a tube furnace. Heating to 950 ℃ at a heating rate of 2 ℃/min under the atmosphere of 5% hydrogen/argon gas mixture, preserving heat for 2h, and naturally cooling to room temperature. And obtaining the nitrogen-doped porous carbon-supported PtCu alloy composite material (hereinafter referred to as PtNi alloy catalyst).
The following are the electrocatalytic oxygen reduction reaction performance tests for the samples prepared in example 3:
As shown in FIG. 4, the prepared PtNi alloy catalyst shows good oxygen reduction catalytic performance in 0.1M HClO 4, the limiting current density reaches 5.8 mA.cm -2, and the half-wave potential reaches 0.920V.
Example 4
The main difference between this embodiment and embodiment 1 is that: the chloride salt cobalt chloride was replaced with ferric chloride. The method comprises the following specific steps:
(a) The procedure was the same as in example 1.
(B) The procedure was the same as in example 1.
(C) Adding 100mg of N-doped porous carbon into 300ml of deionized water, and performing ultrasonic dispersion; subsequently, 90mg of sodium chloroplatinate and 56mg of ferric chloride were added, stirred for 10 hours, and further dispersed by ultrasonic waves for 1 hour. The water was removed by rotary evaporator to give a mixture of supported metal salts.
(D) Transferring the mixture into a corundum porcelain boat, and putting the corundum porcelain boat into a tube furnace. Heating to 900 ℃ at a heating rate of 2 ℃/min under the atmosphere of 5% hydrogen/argon gas mixture, preserving heat for 2h, and naturally cooling to room temperature. And obtaining the nitrogen-doped porous carbon-supported PtFe alloy composite material (hereinafter referred to as PtFe alloy catalyst).
The following are the electrocatalytic oxygen reduction reaction performance tests for the samples prepared in example 4:
As shown in FIG. 4, the prepared PtFe alloy catalyst shows good oxygen reduction catalytic performance in 0.1M HClO 4, the limiting current density reaches 5.8mA.cm -2, and the half-wave potential reaches 0.932V.
As can be seen from fig. 4, the PtCo alloy catalyst of example 1 has the best oxygen reduction performance. PtCo alloy catalyst is selected as cathode catalyst of fuel cell, and the power density of fuel cell reaches 976mW cm -2 (as shown in figure 5), and compared with commercial 70% Pt/C (power density is 808mW cm -2), the fuel cell has great improvement. The catalyst developed by the invention has the prospect of replacing commercial Pt/C catalyst, and provides a new idea for the development of high-efficiency catalyst.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (10)
1. The preparation method of the porous carbon-based platinum catalyst with high specific surface area is characterized by comprising the following steps of:
(1) Mixing 2-aminobenzimidazole and zinc chloride, placing the mixture in a sealed quartz tube, placing the quartz tube in a muffle furnace, and carrying out molten salt reaction under high temperature conditions;
(2) After the reaction in the step (1) is finished and cooled to room temperature, grinding the obtained solid, washing with water and ethanol, and drying in vacuum; then, carrying out high-temperature pyrolysis treatment on the dried material in an inert atmosphere to obtain nitrogen-doped porous carbon;
(3) Dispersing the nitrogen doped porous carbon obtained in the step (2) in an aqueous solution, adding precursors of platinum salt and transition metal salt, stirring, distilling under reduced pressure, drying, transferring to a tube furnace, and calcining at high temperature to obtain the porous carbon-based platinum catalyst with high specific surface area.
2. The method for preparing a porous carbon-based platinum catalyst with high specific surface area according to claim 1, wherein in the step (1), the mass ratio of 2-aminobenzimidazole to zinc chloride is 1:5.
3. The method for preparing a porous carbon-based platinum catalyst having a high specific surface area according to claim 1, wherein in the step (1), the molten salt is reacted at a temperature of 600 to 900 ℃ for 40 hours.
4. The method for preparing a porous carbon-based platinum catalyst having a high specific surface area according to claim 1, wherein in the step (1), 2-aminobenzimidazole and zinc chloride are transferred into a quartz tube by being sufficiently ground in a glove box.
5. The method for preparing a porous carbon-based platinum catalyst having a high specific surface area according to claim 1, wherein in the step (2), the high-temperature pyrolysis is performed at a temperature of 800 to 1000 ℃ for a time of 2 to 5 hours.
6. The method for preparing a porous carbon-based platinum catalyst with a high specific surface area according to claim 1, wherein in the step (3), the platinum salt is chloroplatinic acid, and the transition metal salt is one or more of cobalt chloride, copper chloride, ferric chloride and nickel chloride.
7. The method for preparing a porous carbon-based platinum catalyst having a high specific surface area according to claim 1, wherein in the step (3), the atmosphere of high-temperature calcination is 5% of an H 2/Ar mixed gas.
8. The method for preparing a porous carbon-based platinum catalyst having a high specific surface area according to claim 1, wherein in the step (3), the high-temperature calcination is performed at 600 to 1000 ℃ for 2 to 5 hours.
9. A high specific surface area porous carbon-based platinum catalyst prepared by the method of any one of claims 1-8.
10. Use of a high specific surface area porous carbon-based platinum catalyst prepared according to the preparation method of any one of claims 1 to 8 as an electrocatalytic oxygen reduction electrocatalyst in a fuel cell.
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