CN111987322A - Novel Pt-Co/NC catalyst and preparation method and application thereof - Google Patents
Novel Pt-Co/NC catalyst and preparation method and application thereof Download PDFInfo
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- CN111987322A CN111987322A CN202010803369.1A CN202010803369A CN111987322A CN 111987322 A CN111987322 A CN 111987322A CN 202010803369 A CN202010803369 A CN 202010803369A CN 111987322 A CN111987322 A CN 111987322A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 238000000935 solvent evaporation Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- 239000000725 suspension Substances 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 43
- 239000007787 solid Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011858 nanopowder Substances 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052697 platinum Inorganic materials 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000002923 metal particle Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000026058 directional locomotion Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/9041—Metals or alloys
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a novel Pt-Co/NC catalyst, a preparation method and application thereof. In a fuel cell, the catalyst in the membrane electrode is easily contacted with the reactant oxygen, and the coordinated catalytic action between platinum and cobalt improves ORR activity and durability. The main active components of the catalyst are Pt and Co which are prepared by means of coprecipitation, high-temperature roasting, solvent evaporation and the like, and the preparation method is simple and convenient to operate. According to the Pt-Co/NC catalyst, the porous carbon NC after acid etching is used for providing a good loading surface and pore channels for metal particles, and platinum metal can be uniformly distributed; the nitrogen-doped carbon can activate ORR (oxygen reduction) reaction, indirectly play a role of replacing rare noble metal platinum, is beneficial to manufacturing low-price fuel cells with low manufacturing environmental load, and is more beneficial to promoting global energy distribution and development under the condition of not being controlled by resources.
Description
Technical Field
The invention relates to the technical field of fuel cell catalysts, in particular to a novel Pt-Co/NC (nitrogen-doped porous carbon) catalyst and a preparation method and application thereof.
Background
The increasingly serious environmental problems caused by the gradual exhaustion and unreasonable utilization of fossil energy make people have to develop and search a novel green energy. The hydrogen energy source, as the most clean and environment-friendly energy source so far, has the advantages of high energy conversion rate, non-toxicity and harmlessness of high products and the like, the most important utilization mode is to use the hydrogen energy source in a fuel cell to convert chemical energy into electric energy, and compared with the energy conversion efficiency of 10% -30% of an energy combustion engine, the hydrogen fuel cell is not limited by Carnot cycle, so that the actual energy conversion efficiency can reach 60-80%.
For hydrogen fuel cells, electrodes (coated with platinum/carbon catalyst) and proton exchange membranes are important components, and carbon serves as a carrier and also serves as an electron transport component. The hydrogen is discharged to the anode of the fuel cell through the air port, the hydrogen is dissociated into two protons and two electrons on the surface of the platinum-carbon electrode, the protons reach the cathode through the proton exchange membrane and then react with the oxygen to generate water, and the electrons which can not pass through the proton exchange membrane need to reach the cathode through an external circuit. The directional movement of the electrons creates an electric current, which generates electrical energy.
Currently, platinum/carbon catalysts have problems of high cost and low stability in fuel cells. The granularity, the particle size distribution, the loading amount and the content of non-platinum components of the platinum in the catalytic center of the platinum-carbon electrode all obviously influence the performance and the service life of the catalyst in chemical reaction. It has been reported that platinum metal particles having a size of 2-5nm and uniformly distributed on carbon, and having a low content of harmful impurities (e.g., chlorine), exhibit superior activity and stability. However, the price of the nano-grade rare noble metal platinum is higher, and the production cost of the platinum/carbon catalyst is greatly increased.
Meanwhile, studies have also shown that incorporation of a trace amount of nitrogen atoms into a carbon material contributes to an active electrode catalyst that promotes oxygen reduction, one of the key steps of a fuel cell. Therefore, there is an urgent need to develop a nitrogen-doped platinum-carbon catalyst with high dispersion and uniform dispersion, which is applied to an electrode material of a fuel cell to contribute to the stability and the service life of the fuel cell.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a novel Pt-Co/NC catalyst which is used for an electrode material in a fuel cell and can reduce the cost of the electrode material in the fuel cell.
Another object of the present invention is to provide a method for preparing the above Pt-Co/NC catalyst and its application in fuel cells.
The technical scheme adopted by the invention is as follows: a preparation method of a novel Pt-Co/NC catalyst comprises the following steps:
s1, dissolving 25-27 parts of 2-methylimidazole and 6-7 parts of triethylamine in 590-610 parts of water, and sequentially performing ultrasonic treatment for 2-5min at room temperature and stirring for 10-30min to obtain a clear suspension A; dissolving 5-40 parts of cobalt salt in 190-210 parts of water, and stirring at room temperature for 5-10min to obtain a solution B;
s2, preparation of a suspension: adding the solution B into the suspension A at room temperature, stirring the suspension A by utilizing magnetons while adding, stirring the obtained mixed solution for 0.5-2h at room temperature, and then continuously stirring for 5-24h at 20-25 ℃ to obtain a suspension C;
s3, coprecipitation: standing the suspension C, layering the suspension C up and down, removing the upper layer, carrying out high-speed centrifugal washing and separation on the suspension C at the lower layer, and then carrying out vacuum drying to obtain a solid D;
s4, high-temperature roasting: placing the solid D in a tube furnace, roasting at 350-900 ℃ under the protection of inert gas, and naturally cooling after roasting and heat preservation for 1-5 h; after roasting, washing and drying to obtain carbonized porous solid E;
s5, dissolving the porous solid E in water, dropwise adding a dilute nitric acid solution into the solution, uniformly stirring at room temperature, centrifuging, washing the mixed solution, and drying in vacuum to obtain a solid F;
s6, solvent evaporation: dissolving 0.1-1 part of solid F in 39-41 parts of methanol, ultrasonically dividing 0.1-2 parts of sodium hydroxyplatinate into 7-9 parts of methanol, dropwise adding 9-11 parts of 0.5M sodium borohydride aqueous solution, adding the obtained solution into the solution containing the solid F to obtain a mixed solution, heating in a water bath until the methanol is evaporated to dryness, and sequentially washing, vacuum-drying and obtaining the platinum-cobalt/porous carbon nano powder.
Preferably, in step S1, the cobalt salt is selected from one or a combination of two of cobalt nitrate hexahydrate and cobalt acetate.
Preferably, in step S1, the magnetons are magnetically stirred at a stirring speed of 300-800 rmp/min.
Preferably, in the step S3, the vacuum drying temperature is 40-80 ℃, and the drying time is 10-12 h.
Preferably, the water in the steps S1, S5 and S6 is deionized water, and the methanol and ethanol are industrial grade with purity of 98%.
Preferably, in the ultrasonic dispersion process of the steps S1 and S6, the ultrasonic frequency is 50-150kHz, 80-150kHz or 100-150 kHz; the ultrasonic time range of the step S6 is 10-30 min.
Preferably, in the step S4, the heating rate is 1-2 ℃, 3-5 ℃ or 5-10 ℃/min; the calcination time is 1-5h, 1-3h or 4-5h (the rate of temperature rise decreases with the increase in sample mass).
Preferably, in step S4, the inert gas is high-purity nitrogen, high-purity argon, or hydrogen in argon (5% H)2) One of (1) and (b).
Preferably, in the steps S3 and S5, the centrifugal washing step is: the sample is washed and centrifuged for three times by water and ethanol sequentially, and the centrifugation speed is 5000-10000 rmp/min.
Preferably, in step S6, the water bath heating operation includes: placing the mixed solution in a water bath kettle at 50-60 ℃, heating and stirring until methanol is evaporated to dryness; the specific operation of washing and vacuum drying is as follows: washing with water and ethanol for three times in sequence, and vacuum drying at 50 ℃ to obtain the platinum-cobalt/porous carbon nano powder.
Preferably, in step S5, the concentration of the dilute nitric acid solution is 1g/ml, and the ratio of the porous solid E: water: the quantity ratio of the dilute nitric acid solution is 0.5: 1: 1.
a novel Pt-Co/NC catalyst, the product prepared according to the above preparation method.
The application of the novel Pt-Co/NC catalyst is the application of the novel Pt-Co/NC catalyst in the fuel cell electrode.
Compared with the prior art, the invention has the following advantages:
(1) according to the Pt-Co/NC catalyst, the porous carbon NC after acid etching is used for providing a good loading surface and pore channels for metal particles, platinum metal can be uniformly distributed, and meanwhile, the carbon has good thermal conductivity and electron transport property, so that the problem of nonuniform heating of metal can be solved, and the electronic migration in the reforming redox reaction is facilitated.
(2) The nitrogen-doped carbon can activate ORR (oxygen reduction) reaction, indirectly play a role of replacing rare noble metal platinum, is beneficial to manufacturing low-price fuel cells with low manufacturing environmental load, and is more beneficial to promoting global energy distribution and development under the condition of not being controlled by resources.
(3) The Pt-Co/NC catalyst provided by the invention has nitrogen-doped carbon as a carrier, metal Co (cobalt) as an auxiliary catalyst and noble metal Pt (platinum) as a main catalyst. In a fuel cell, the catalyst in the membrane electrode is easily contacted with the reactant oxygen, and the coordinated catalytic action between platinum and cobalt improves ORR activity and durability.
The specific implementation mode is as follows:
in order to enhance the understanding of the present invention, the present invention will be described in further detail with reference to embodiments. The invention can be implemented by:
example 1
A preparation method of a novel Pt-Co/NC catalyst comprises the following steps:
s1, dissolving 26g of 2-methylimidazole and 6.5g of triethylamine in a beaker filled with 600 milliliters of water, and sequentially carrying out ultrasonic treatment for 2min and stirring for 30min at room temperature to obtain a clear suspension A; 8.62g of cobalt acetate was dissolved in a beaker containing 200 ml of the aqueous solution, and stirred at room temperature for 10min to obtain a solution B.
S2, adding the solution B into the suspension A at room temperature, stirring the suspension A by utilizing magnetons while adding, stirring the obtained mixed solution for 1h at room temperature, and then continuously stirring for 12h at 25 ℃ to obtain a suspension C.
S3, standing the suspension C, then layering the suspension C up and down, removing the upper layer, moving the lower layer suspension into a centrifuge tube, putting the centrifuge tube into a centrifuge for high-speed centrifugal separation, washing the suspension with water and ethanol for three times during centrifugation, then placing the suspension in a vacuum drying box, setting the vacuum drying temperature at 50 ℃, and drying for 11 hours to obtain a solid D.
S4, placing the solid D in a tube furnace, and carrying out hydrogen (5% H) in argon2) Roasting at 700 ℃ under the atmosphere protection condition, wherein the heating rate is 5 ℃/min. And washing and drying the roasted sample to obtain a carbonized porous solid E.
S5, dissolving 2g of solid E in 50ml of water, dropwise adding 5ml of 0.01M dilute nitric acid solution into the solution, stirring for 2min at room temperature, centrifuging, washing the mixed solution, and drying in vacuum to obtain solid F.
S6, dissolving 0.8g of solid F in 50ml of methanol, ultrasonically dispersing 0.3g of sodium hydroxyplatinate (100kHz) in 10ml of methanol, dropwise adding 10ml of 0.5M sodium borohydride aqueous solution, adding the obtained solution into the solution containing the solid F, heating and stirring at 55 ℃ until the methanol is evaporated to dryness, and washing, vacuum drying and obtaining the Pt-Co/NC.
Example 2
S1, dissolving 26g of 2-methylimidazole and 6.5g of triethylamine in a beaker filled with 600 milliliters of water, and carrying out ultrasonic treatment for 2min and stirring for 30min at room temperature in sequence to obtain a clear suspension A. 8.62g of cobalt acetate was dissolved in a beaker containing 200 ml of the aqueous solution, and stirred at room temperature for 10min to obtain a solution B.
S2, adding the solution B into the suspension A at room temperature, stirring the suspension A by utilizing magnetons while adding, stirring the obtained mixed solution for 1h at room temperature, and then continuously stirring for 12h at 25 ℃ to obtain a suspension C.
S3, standing the suspension C, then layering the suspension C up and down, removing the upper layer, moving the lower layer suspension into a centrifuge tube, putting the centrifuge tube into a centrifuge for high-speed centrifugal separation, washing the suspension C three times with water and ethanol in sequence during centrifugation, and then drying the suspension C in a vacuum drying oven at a certain temperature to obtain a solid D.
S4, placing the solid D in a tubular furnace, and roasting at 700 ℃ under the protection of hydrogen atmosphere in argon at the heating rate of 5 ℃/min. And washing and drying the roasted sample to obtain a carbonized porous solid E.
S5, dissolving 2g of solid E in 50ml of water, dropwise adding 5ml of 0.05M dilute nitric acid solution into the solution, stirring for 2min at room temperature, centrifuging, washing the mixed solution, and drying the sample in vacuum to obtain solid F.
S6.S6. taking 0.8g of solid F to dissolve in 50ml of methanol, ultrasonically dispersing 0.3g of sodium hydroxyplatinate (100kHz) in 10ml of methanol, dropwise adding 10ml of 0.5M sodium borohydride aqueous solution to obtain a solution, adding the solution into the solution, heating at 55 ℃, stirring until the methanol is evaporated to dryness, and obtaining the product Pt-Co/NC.
Example 3
S1, dissolving 26g of 2-methylimidazole and 6.5g of triethylamine in a beaker filled with 600 milliliters of water, and carrying out ultrasonic treatment for 2min and stirring for 30min at room temperature in sequence to obtain a clear suspension A. 8.62g of cobalt acetate was dissolved in a beaker containing 200 ml of the aqueous solution, and stirred at room temperature for 10min to obtain a solution B.
S2, adding the solution B into the suspension A at room temperature, stirring the suspension A by utilizing magnetons while adding, stirring the obtained mixed solution for 1h at room temperature, and then continuously stirring for 12h at 25 ℃ to obtain a suspension C.
S3, standing the suspension C, then layering the suspension C up and down, removing the upper layer, moving the lower layer suspension into a centrifuge tube, putting the centrifuge tube into a centrifuge for high-speed centrifugal separation, washing the suspension C three times with water and ethanol in sequence during centrifugation, and then drying the suspension C in a vacuum drying oven at a certain temperature to obtain a solid D.
S4, placing the solid D in a tubular furnace, and roasting at 800 ℃ under the protection of hydrogen atmosphere in argon at the heating rate of 5 ℃/min. And washing and drying the roasted sample to obtain a carbonized porous solid E.
S5, dissolving 2g of solid E in 50ml of water, dropwise adding 5ml of 0.01M dilute nitric acid solution into the solution, stirring for 2min at room temperature, centrifuging, washing the mixed solution, and drying the sample in vacuum to obtain solid F.
S6.S6. taking 0.8g of solid F to dissolve in 50ml of methanol, ultrasonically dispersing 0.3g of sodium hydroxyplatinate (100kHz) in 10ml of methanol, dropwise adding 10ml of 0.5M sodium borohydride aqueous solution to obtain a solution, adding the solution into the solution, heating at 55 ℃, stirring until the methanol is evaporated to dryness, and obtaining the product Pt-Co/NC.
Example 4
S1, dissolving 26g of 2-methylimidazole and 6.5g of triethylamine in a beaker filled with 600 milliliters of water, and carrying out ultrasonic treatment for 2min and stirring for 30min at room temperature in sequence to obtain a clear suspension A. 8.62g of cobalt acetate was dissolved in a beaker containing 200 ml of the aqueous solution, and stirred at room temperature for 10min to obtain a solution B.
S2, adding the solution B into the suspension A at room temperature, stirring the suspension A by utilizing magnetons while adding, stirring the obtained mixed solution for 1h at room temperature, and then continuously stirring for 12h at 25 ℃ to obtain a suspension C.
S3, standing the suspension C, then layering the suspension C up and down, removing the upper layer, moving the lower layer suspension into a centrifuge tube, putting the centrifuge tube into a centrifuge for high-speed centrifugal separation, washing the suspension C three times with water and ethanol in sequence during centrifugation, and then drying the suspension C in a vacuum drying oven at a certain temperature to obtain a solid D.
S4, placing the solid D in a tubular furnace, and roasting at 800 ℃ under the protection of hydrogen atmosphere in argon at the heating rate of 5 ℃/min. And washing and drying the roasted sample to obtain a carbonized porous solid E.
S5, dissolving 2g of solid E in 50ml of water, dropwise adding 5ml of 0.05M dilute nitric acid solution into the solution, stirring for 2min at room temperature, centrifuging, washing the mixed solution, and drying the sample in vacuum to obtain solid F.
S6.S6. taking 0.8g of solid F to dissolve in 50ml of methanol, ultrasonically dispersing 0.3g of sodium hydroxyplatinate (100kHz) in 10ml of methanol, dropwise adding 10ml of 0.5M sodium borohydride aqueous solution to obtain a solution, adding the solution into the solution, heating at 55 ℃, stirring until the methanol is evaporated to dryness, and obtaining the product Pt-Co/NC.
Examples 1 to 4 are different in the calcination temperature in the S4 step and the dilute nitric acid solution concentration in the S5 step.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a novel Pt-Co/NC catalyst is characterized by comprising the following steps:
s1, dissolving 25-27 parts of 2-methylimidazole and 6-7 parts of triethylamine in 590-610 parts of water, and sequentially performing ultrasonic treatment for 2-5min at room temperature and stirring for 10-30min to obtain a clear suspension A; dissolving 5-40 parts of cobalt salt in 190-210 parts of water, and stirring at room temperature for 5-10min to obtain a solution B;
s2, preparation of a suspension: adding the solution B into the suspension A at room temperature, stirring the suspension A by utilizing magnetons while adding, stirring the obtained mixed solution for 0.5-2h at room temperature, and then continuously stirring for 5-24h at 20-25 ℃ to obtain a suspension C;
s3, coprecipitation: standing the suspension C, layering the suspension C up and down, removing the upper layer, carrying out high-speed centrifugal washing and separation on the suspension C at the lower layer, and then carrying out vacuum drying to obtain a solid D;
s4, high-temperature roasting: placing the solid D in a tube furnace, roasting at 350-900 ℃ under the protection of inert gas, and naturally cooling after roasting and heat preservation for 1-5 h; after roasting, washing and drying to obtain carbonized porous solid E;
s5, dissolving the porous solid E in water, dropwise adding a dilute nitric acid solution into the solution, uniformly stirring at room temperature, centrifuging, washing the mixed solution, and drying in vacuum to obtain a solid F;
s6, solvent evaporation: dissolving 0.1-1 part of solid F in 39-41 parts of methanol, ultrasonically dividing 0.1-2 parts of sodium hydroxyplatinate into 7-9 parts of methanol, dropwise adding 9-11 parts of 0.5M sodium borohydride aqueous solution, adding the obtained solution into the solution containing the solid F to obtain a mixed solution, heating in a water bath until the methanol is evaporated to dryness, and sequentially washing, vacuum-drying and obtaining the platinum-cobalt/porous carbon nano powder.
2. The method of claim 1, wherein in step S1, the cobalt salt is selected from one or a combination of two of cobalt nitrate hexahydrate and cobalt acetate.
3. The method for preparing a novel Pt-Co/NC catalyst according to claim 1, wherein in the ultrasonic dispersion process of the steps S1 and S6, the ultrasonic frequency is 50-150kHz, 80-150kHz or 100-150 kHz; the ultrasonic time range of the step S6 is 10-30 min.
4. The method for preparing a novel Pt-Co/NC catalyst according to claim 1, wherein in the step S4, the temperature rise rate is 1-2 ℃, 3-5 ℃ or 5-10 ℃/min; the roasting time is 1-5h, 1-3h or 4-5 h.
5. The method of claim 1, wherein in step S4, the inert gas is selected from the group consisting of high purity nitrogen, high purity argon, and hydrogen in argon (5% H)2) One of (1) and (b).
6. The method for preparing a novel Pt-Co/NC catalyst according to claim 1, wherein in the steps S3 and S5, the centrifugal washing step is: the sample is washed and centrifuged for three times by water and ethanol sequentially, and the centrifugation speed is 5000-10000 rmp/min.
7. The method of claim 1, wherein in step S5, the concentration of the dilute nitric acid solution is 1 g/ml.
8. The method for preparing a novel Pt-Co/NC catalyst according to claim 1, wherein in the step S6, the water bath heating operation comprises: placing the mixed solution in a water bath kettle at 50-60 ℃, heating and stirring until methanol is evaporated to dryness; the specific operation of washing and vacuum drying is as follows: washing with water and ethanol for three times in sequence, and vacuum drying at 50 ℃ to obtain the platinum-cobalt/porous carbon nano powder.
9. A novel Pt-Co/NC catalyst characterized by the product prepared by the preparation method according to any one of claims 1 to 8.
10. Use of a novel Pt-Co/NC catalyst, characterized by the use of the novel Pt-Co/NC catalyst according to claim 9 in a fuel cell electrode.
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