CN113745555A - Device and method for preparing carbon-supported platinum nano catalyst by solid phase mixing - Google Patents
Device and method for preparing carbon-supported platinum nano catalyst by solid phase mixing Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000002156 mixing Methods 0.000 title claims abstract description 85
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 39
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000007790 solid phase Substances 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 133
- 239000002243 precursor Substances 0.000 claims abstract description 113
- 239000011259 mixed solution Substances 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 24
- 239000011343 solid material Substances 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 17
- 239000000969 carrier Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
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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
-
- 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
Abstract
The invention discloses a device and a method for preparing a carbon-supported platinum nano catalyst by solid-phase mixing. The device comprises a precursor solution tank, a solution mixing device, a mixed solution tank and a charging bucket which are sequentially connected through a pipeline and a pump, wherein the solution mixing device is provided with a spiral pipeline, and the charging bucket is placed inside the solid material mixing device. The using method comprises the following steps: the precursor solution is fully mixed with ultrasonic treatment through a spiral pipeline, carbon carriers are added into the precursor mixed solution or the precursor mixed solution is added into the carbon carriers under the stirring state for ultrasonic pretreatment, and the mixture is stirred, mixed, dried, reduced and sintered, cleaned and dried again. Compared with the prior art, the method has the advantages of simple and controllable operation process and short period, does not need to add an organic surfactant and a complexing agent, can be used for filtering and cleaning by pure water, does not generate a large amount of polluted waste liquid, can realize batch continuous production of the high-load PtC catalyst, and is suitable for large-scale preparation of the PtC catalyst for commercial application.
Description
Technical Field
The invention belongs to the technical field of fuel cell catalyst materials, and particularly relates to a device and a method for preparing a carbon-supported platinum nano catalyst by solid-phase mixing.
Background
The fuel cell takes hydrogen as fuel, has the outstanding advantages of high energy density, long endurance, cleanness, environmental protection and the like, is considered as the most ideal new energy technology in the 21 st century, and has wide application prospect in the fields of automobiles, energy storage and the like. The main action mechanism of the fuel cell is to convert the chemical energy of the reaction of hydrogen and oxygen into electric energy through electrochemical reaction, the kinetics of the process is very slow, a large amount of platinum (Pt) containing catalyst is needed to accelerate the reaction, and the energy conversion efficiency is improved, so the catalyst is an indispensable key material, the current commercial fuel cell catalyst is a carbon-supported platinum (PtC) based catalyst, the low-cost and high-performance large-scale preparation of the PtC catalyst is carried out through a simple and environment-friendly process and device, and the key is to accelerate and popularize the commercial application of the fuel cell.
When preparing the PtC catalyst, the size and dispersion of catalyst particles are key, and meanwhile, the high loading (more than 20 percent of Pt metal content) is ensured, the utilization rate of the noble metal Pt is improved, the cost is reduced, and the method is the mainstream direction of commercial application. At present, the preparation methods of the PtC catalyst can be divided into two main types, liquid phase method and solid phase method. The liquid phase method needs to add a reducing agent and a surfactant for treatment, so that Pt nanoparticles are reduced and adsorbed on the surface of a carbon carrier, the agglomeration of the particles is avoided, a large amount of aqueous or organic solvent is needed for filtering and cleaning in the subsequent steps, a large amount of organic waste liquid is generated, the filtering efficiency is low, and the large-scale production is not facilitated. The solid phase method mainly comprises the steps of mixing a Pt-containing precursor solution with a carbon carrier, drying and then treating in a reducing atmosphere to obtain PtC particles, and adjusting the precursor solution to be acidic is a common technical means of the solid phase method, and although the means can obtain the Pt particles which are uniformly dispersed, only a lower-loading-capacity (Pt content is less than 10%) PtC catalyst can be prepared due to the principle of electrostatic adsorption, the performance requirements of a commercial fuel cell catalyst cannot be met.
In summary, in the existing methods for preparing PtC catalysts, surfactants or complexing agents are usually added, which not only affects the cleanness of the catalyst surface and is not favorable for catalytic reaction, but also requires a large amount of organic solvent for filtration and cleaning, thereby generating a large amount of polluted waste liquid, and in addition, it is difficult to obtain a high-capacity PtC catalyst, which is not favorable for commercial development.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the device for preparing the carbon-supported platinum nano catalyst by solid-phase mixing is provided, has simple and controllable operation process and short period, can realize the batch continuous production of the high-loading PtC catalyst, and is suitable for preparing the PtC catalyst in a large scale for commercial application.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a device of solid phase mixing preparation carbon carries platinum nanometer catalyst, includes precursor solution jar, solution mixing arrangement, mixed solution jar, the material jar that loops through pipeline and pump connection, solution mixing arrangement is equipped with the spiral pipeline, the material jar is placed inside solid material mixing arrangement.
Preferably, the precursor solution is converged from the precursor solution tank to the solution mixing device and enters the spiral pipe, and the length of the spiral pipe is at least 1 meter.
Preferably, the solution mixing device is internally loaded with an aqueous solution, and is provided with an ultrasonic generator for performing ultrasonic treatment on the precursor solution entering the spiral pipeline.
Preferably, the solid material mixing device is internally loaded with an aqueous solution, an ultrasonic generator is arranged for carrying out ultrasonic treatment on the material in the material tank, and a heater can be arranged for heating the aqueous solution in the internal device, so that the material in the material tank can be heated.
Preferably, the upper part of the solid material mixing device is provided with a cover plate, the bottom of the cover plate is provided with a sliding rail which can slide towards two sides, the material tank can be placed into the solid material mixing device when the material tank is opened, and the material tank can be clamped and fixed when the material tank is closed.
Preferably, the material jar top is uncovered, is equipped with the material jar upper cover and carries out the closing cap, the material jar upper cover pass through the hinge hasp with the material jar is connected.
Preferably, the upper part of the upper cover of the charging bucket is open and used for extending a stirrer of a stirring device into the charging bucket to stir and mix the materials in the charging bucket.
The other purpose of the invention is to use the device of the invention to prepare the carbon-supported platinum nano-catalyst, without adding organic surfactant and complexing agent, and pure water is adopted for filtering and cleaning, and no large amount of polluted waste liquid is generated, which is the method I or the method II;
the first method comprises the following steps:
firstly, respectively adding chloroplatinic acid precursor solution and sodium hydroxide precursor solution with a molar ratio of 1:4-1:9 into a precursor solution tank, converging the solutions into a solution mixing device through a pump, feeding the solutions into a spiral pipeline, starting an ultrasonic device in the solution mixing device, and carrying out ultrasonic treatment on the precursor solution;
secondly, ultrasonically mixing the precursor solution in a solution mixing device, then feeding the precursor solution into a mixed solution tank, starting a pump between the mixed solution tank and a material tank after the precursor mixed solution completely enters the mixed solution tank, and pumping 70-90% of the precursor mixed solution into the material tank;
thirdly, starting a stirrer, and adding the carbon carrier under the state of stirring the precursor mixed solution in the material tank, wherein the rotating speed of the stirrer is 50-150 rpm;
step four, continuously pumping the remaining 10-30% of precursor mixed solution into the material tank, flushing the carbon carriers splashed on the peripheral tank walls of the material tank down, adjusting the rotating speed of the stirrer to 150 plus 250rpm, and continuously stirring for 30-60 min;
fifthly, drying the slurry after stirring, sintering in a reducing atmosphere of H2+ Ar, cleaning and drying again to obtain the carbon-supported platinum nano catalyst;
the second method comprises the following steps:
firstly, respectively adding chloroplatinic acid precursor solution and sodium hydroxide precursor solution with a molar ratio of 1:4-1:9 into a precursor solution tank, converging the solutions into a solution mixing device through a pump, feeding the solutions into a spiral pipeline, starting an ultrasonic device in the solution mixing device, and carrying out ultrasonic treatment on the precursor solution;
secondly, ultrasonically mixing the precursor solution in a solution mixing device, then feeding the precursor solution into a mixed solution tank, and starting a pump between the mixed solution tank and a charging bucket after all the precursor mixed solution enters the mixed solution tank;
thirdly, after the carbon carrier is added into the material tank, starting a pump to completely add the precursor mixed solution in the mixed solution tank into the material tank, and then starting the ultrasonic treatment of the solid material mixing device for 5-15 min;
fourthly, after the ultrasonic treatment is finished, starting the stirrer, and stirring at the rotating speed of 150 plus 250rpm for 20-50 min;
and fifthly, drying the slurry after stirring, sintering in a reducing atmosphere of H2+ Ar, cleaning and drying again to obtain the carbon-supported platinum nano catalyst.
Preferably, the ratio of the carbon carrier to the precursor mixed solution is 30-80g/L, and the volume of the chloroplatinic acid precursor solution is calculated according to the loading amount of Pt in the carbon-supported platinum nano catalyst being 20-60%.
Preferably, the sintering temperature is 200-500 ℃ and the time is 0.5-4h, and the cleaning is performed by adopting an aqueous solution.
Compared with the prior art, the invention has at least the following beneficial effects:
firstly, the preparation device and the preparation method have the advantages of simple operation process, short period, easy amplification and continuous production, no need of using a surfactant or a complexing agent, no organic wastewater pollution, reduction generation of NaCl instead of HCl acidic waste gas, and removal of NaCl after washing, thereby avoiding the poisoning effect of Cl on the Pt catalyst.
Secondly, each part of the device is independent, the device is easy to clean, find and solve problems, the precursor solution is fully ultrasonically mixed in the spiral pipeline and then mixed with the carbon carrier, the carbon carrier is added into the stirred precursor solution, or the ultrasonic treatment is carried out for a short time before the precursor solution and the carbon carrier are stirred, so that the Pt-containing precursor solution is fully contacted and adsorbed with the carbon carrier, the stirring and mixing are carried out to promote the upper amount and uniform dispersion of Pt on the carbon carrier, and the catalytic performance of the catalyst is improved.
And thirdly, the precursor solution consists of chloroplatinic acid and sodium hydroxide with lower cost, is easy to prepare and uniformly mix, and simultaneously, the particle size of the catalyst and the dispersion of Pt can be controlled by adding NaOH, so that the particle size of the catalyst is reduced, and the utilization rate of Pt is improved.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Fig. 2 is (a) a TEM image and (b) an XRD image of the carbon-supported platinum nanocatalyst prepared by the first method of example 1 of the present invention.
FIG. 3 is a graph showing the electrochemical performance of the carbon-supported platinum nanocatalyst prepared by the first method of example 1.
Fig. 4 is (a) a TEM image and (b) an XRD pattern of the platinum-on-carbon nanocatalyst prepared by the second method of example 1 of the present invention.
Fig. 5 is a graph of the electrochemical performance of the carbon supported platinum nanocatalyst prepared by the second method of the example 1 of the present invention.
Detailed Description
The present invention and its advantageous effects will be described in detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
As shown in fig. 1, the present embodiment provides an apparatus for preparing a carbon-supported platinum nanocatalyst by solid-phase mixing, which includes a precursor solution tank 1, a solution mixing device 3, a mixed solution tank 4, and a material tank 5, which are sequentially connected by a pipeline and a pump 2, wherein the solution mixing device 3 is provided with a spiral pipeline 31, and the material tank 5 is placed inside a solid-material mixing device 6.
The precursor solution is collected from a precursor solution tank 1 to a solution mixing device 3 through a pump 2, and enters a spiral pipeline 31, and the length of the spiral pipeline is 1 meter.
The solution mixing device 3 is internally loaded with an aqueous solution and provided with an ultrasonic generator for carrying out ultrasonic treatment on the precursor solution entering the spiral pipeline 31.
The solid material mixing device 6 is internally loaded with water solution and provided with an ultrasonic generator for carrying out ultrasonic treatment on the material in the charging bucket 5.
The upper part of the solid material mixing device 6 is provided with a cover plate 9, the bottom of the cover plate 9 is provided with a slide rail which can slide to two sides, the material tank 5 can be placed into the solid material mixing device 6 when the solid material mixing device is opened, and the fixed material tank 5 can be clamped when the solid material mixing device is closed.
The top of the charging bucket 5 is open, and is provided with a charging bucket upper cover 7 for sealing, and the charging bucket upper cover 7 is connected with the charging bucket 5 through a hinge lock catch.
The upper part of the charging bucket upper cover 7 is open and is used for extending a stirrer of the stirring device 8 into the charging bucket 5 to stir and mix the materials in the charging bucket 5.
The method for preparing the carbon-supported platinum nano-catalyst by using the reaction device comprises the following two methods:
the first method comprises the following steps:
firstly, respectively adding chloroplatinic acid precursor solution and sodium hydroxide precursor solution with a molar ratio of 1:5 into a precursor solution tank, converging the chloroplatinic acid precursor solution and the sodium hydroxide precursor solution into a solution mixing device through a pump, feeding the solution mixing device into a spiral pipeline, starting an ultrasonic device in the solution mixing device, and carrying out ultrasonic treatment on the precursor solution;
secondly, ultrasonically mixing the precursor solution in a solution mixing device, then feeding the precursor solution into a mixed solution tank, starting a pump between the mixed solution tank and a charging bucket after all the precursor mixed solution enters the mixed solution tank, and pumping 80% of the precursor mixed solution into the charging bucket;
thirdly, starting a stirrer, and adding the carbon carrier under the state of stirring the precursor mixed solution in the material tank, wherein the rotating speed of the stirrer is 100 rpm;
step four, continuously pumping the remaining 20% of precursor mixed solution into the charging bucket, flushing the carbon carriers splashed on the peripheral walls of the charging bucket, adjusting the rotating speed of the stirrer to 150rpm, and continuously stirring for 30 min;
fifthly, drying and H processing the slurry after stirring2Sintering, cleaning and drying under the reducing atmosphere of + Ar to obtain the carbon-supported platinum nano catalyst;
the second method comprises the following steps:
firstly, respectively adding chloroplatinic acid precursor solution and sodium hydroxide precursor solution with a molar ratio of 1:5 into a precursor solution tank, converging the chloroplatinic acid precursor solution and the sodium hydroxide precursor solution into a solution mixing device through a pump, feeding the solution mixing device into a spiral pipeline, starting an ultrasonic device in the solution mixing device, and carrying out ultrasonic treatment on the precursor solution;
secondly, ultrasonically mixing the precursor solution in a solution mixing device, then feeding the precursor solution into a mixed solution tank, and starting a pump between the mixed solution tank and a charging bucket after all the precursor mixed solution enters the mixed solution tank;
thirdly, after the carbon carrier is added into the material tank, starting a pump to completely add the precursor mixed solution in the mixed solution tank into the material tank, and then starting the ultrasonic treatment of the solid material mixing device for 10 min;
fourthly, after the ultrasonic treatment is finished, starting a stirrer, and stirring at the rotating speed of 150rpm for 20 min;
fifthly, drying and H processing the slurry after stirring2And (5) sintering, cleaning and drying in the reducing atmosphere of + Ar to obtain the carbon-supported platinum nano catalyst.
Wherein the ratio of the carbon carrier to the precursor mixed solution is 50g/L, and the volume of the chloroplatinic acid precursor solution is calculated according to the loading amount of Pt in the carbon-supported platinum nano catalyst being 40%.
The sintering temperature is 300 ℃, the time is 1h, and the cleaning adopts aqueous solution.
As shown in FIG. 2, the platinum on carbon nano-catalyst particles prepared by the first example method were uniformly dispersed, and the catalyst particles had a size of about 3.5nm and a fine size, calculated on the basis of Pt (111). The electrochemically active area of the catalyst obtained from FIG. 3 was 61 m2/gPtMass activity measured at 0.9V vs. RHE of 0.16A/mgPtSpecific area activity of about 0.26 mA/cm2 Pt。
Fig. 4 is a TEM and XRD chart of the carbon-supported platinum nano-catalyst prepared by the second process of this example, in which the particles of the catalyst are uniformly dispersed and have a fine size of about 3.6 nm. FIG. 5 is a graph showing the electrochemical performance of the catalyst, and the electrochemical active area is 59 m2/gPtMass measured at 0.9V vs. RHEThe quantitative activity was 0.15A/mgPtSpecific area activity of about 0.26 mA/cm2 Pt。
Example 2
Different from the embodiment 1, the preparation method of the carbon-supported platinum nano-catalyst comprises the following steps:
firstly, respectively adding chloroplatinic acid precursor solution and sodium hydroxide precursor solution with a molar ratio of 1:6 into a precursor solution tank, converging the chloroplatinic acid precursor solution and the sodium hydroxide precursor solution into a solution mixing device through a pump, feeding the solution mixing device into a spiral pipeline, starting an ultrasonic device in the solution mixing device, and carrying out ultrasonic treatment on the precursor solution;
secondly, ultrasonically mixing the precursor solution in a solution mixing device, then feeding the precursor solution into a mixed solution tank, starting a pump between the mixed solution tank and a material tank after the precursor mixed solution completely enters the mixed solution tank, and pumping 90% of the precursor mixed solution into the material tank;
thirdly, starting a stirrer, and adding the carbon carrier under the state of stirring the precursor mixed solution in the material tank, wherein the rotating speed of the stirrer is 120 rpm;
step four, continuously pumping the remaining 10% of precursor mixed solution into the charging bucket, flushing the carbon carriers splashed on the peripheral walls of the charging bucket, adjusting the rotating speed of the stirrer to 200rpm, and continuously stirring for 45 min;
fifthly, drying and H processing the slurry after stirring2Sintering, cleaning and drying under the reducing atmosphere of + Ar to obtain the carbon-supported platinum nano catalyst;
wherein, the ratio of the carbon carrier to the precursor mixed solution is 60g/L, and the volume of the chloroplatinic acid precursor solution is calculated according to the 60 percent of the loading amount of Pt in the carbon-supported platinum nano catalyst.
The sintering temperature is 250 ℃, the time is 2 hours, and the cleaning adopts aqueous solution.
Example 3
Different from the embodiment 1, the preparation method of the carbon-supported platinum nano-catalyst comprises the following steps:
firstly, respectively adding chloroplatinic acid precursor solution and sodium hydroxide precursor solution with a molar ratio of 1:8 into a precursor solution tank, converging the chloroplatinic acid precursor solution and the sodium hydroxide precursor solution into a solution mixing device through a pump, feeding the solution mixing device into a spiral pipeline, starting an ultrasonic device in the solution mixing device, and carrying out ultrasonic treatment on the precursor solution;
secondly, ultrasonically mixing the precursor solution in a solution mixing device, then feeding the precursor solution into a mixed solution tank, and starting a pump between the mixed solution tank and a charging bucket after all the precursor mixed solution enters the mixed solution tank;
thirdly, after the carbon carrier is added into the material tank, starting a pump to completely add the precursor mixed solution in the mixed solution tank into the material tank, and then starting the ultrasonic treatment of the solid material mixing device for 5 min;
fourthly, after the ultrasonic treatment is finished, starting a stirrer, and stirring for 30min at the rotating speed of 180 rpm;
fifthly, drying and H processing the slurry after stirring2And (5) sintering, cleaning and drying in the reducing atmosphere of + Ar to obtain the carbon-supported platinum nano catalyst.
Wherein, the ratio of the carbon carrier to the precursor mixed solution is 70g/L, and the volume of the chloroplatinic acid precursor solution is calculated according to the loading amount of Pt in the carbon-supported platinum nano catalyst being 20 percent.
The sintering temperature is 500 ℃, the time is 0.5h, and the cleaning adopts aqueous solution.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The device for preparing the carbon-supported platinum nano-catalyst through solid-phase mixing is characterized by comprising a precursor solution tank, a solution mixing device, a mixed solution tank and a material tank which are sequentially connected through a pipeline and a pump, wherein the solution mixing device is provided with a spiral pipeline, and the material tank is placed inside the solid-material mixing device.
2. The apparatus for preparing carbon-supported platinum nanocatalyst by solid phase mixing as claimed in claim 1, wherein a precursor solution is collected from the precursor solution tank to the solution mixing device and enters the spiral pipe, and the length of the spiral pipe is at least 1 meter.
3. The apparatus for preparing carbon-supported platinum nanocatalyst by solid phase mixing according to claim 1, wherein the solution mixing apparatus is loaded with an aqueous solution, and is provided with an ultrasonic generator for performing ultrasonic treatment on the precursor solution entering the spiral pipeline.
4. The apparatus for preparing a carbon-supported platinum nanocatalyst through solid-phase mixing according to claim 1, wherein the solid-material mixing device is internally loaded with an aqueous solution, and is provided with an ultrasonic generator for performing ultrasonic treatment on the material in the material tank, and is further provided with a heater for heating the aqueous solution in the internal device, thereby heating the material in the material tank.
5. The apparatus for preparing carbon-supported platinum nanocatalyst by solid-phase mixing according to claim 1, wherein a cover plate is arranged on the upper part of the solid-material mixing device, a slide rail is arranged on the bottom of the cover plate and can slide towards two sides, the charging bucket can be placed into the solid-material mixing device when the charging bucket is opened, and the charging bucket can be clamped and fixed when the charging bucket is closed.
6. The apparatus for preparing carbon-supported platinum nanocatalyst by solid phase mixing as claimed in claim 1, wherein the top of the charging bucket is open, and is covered by a charging bucket top cover, and the charging bucket top cover is connected with the charging bucket by a hinge lock catch.
7. The apparatus for preparing carbon-supported platinum nanocatalyst by solid phase mixing as claimed in claim 6, wherein the upper part of the upper cover of the charging bucket is open for extending the stirrer of the stirring device into the charging bucket to stir and mix the materials in the charging bucket.
8. A method for preparing a carbon-supported platinum nanocatalyst using the apparatus of any one of claims 1-7, wherein one of the following two methods is used;
the first method comprises the following steps:
firstly, respectively adding chloroplatinic acid precursor solution and sodium hydroxide precursor solution with a molar ratio of 1:4-1:9 into a precursor solution tank, converging the solutions into a solution mixing device through a pump, feeding the solutions into a spiral pipeline, starting an ultrasonic device in the solution mixing device, and carrying out ultrasonic treatment on the precursor solution;
secondly, ultrasonically mixing the precursor solution in a solution mixing device, then feeding the precursor solution into a mixed solution tank, starting a pump between the mixed solution tank and a material tank after the precursor mixed solution completely enters the mixed solution tank, and pumping 70-90% of the precursor mixed solution into the material tank;
thirdly, starting a stirrer, and adding the carbon carrier under the state of stirring the precursor mixed solution in the material tank, wherein the rotating speed of the stirrer is 50-150 rpm;
step four, continuously pumping the remaining 10-30% of precursor mixed solution into the material tank, flushing the carbon carriers splashed on the peripheral tank walls of the material tank down, adjusting the rotating speed of the stirrer to 150 plus 250rpm, and continuously stirring for 30-60 min;
fifthly, drying and H processing the slurry after stirring2Sintering, cleaning and drying under the reducing atmosphere of + Ar to obtain the carbon-supported platinum nano catalyst;
the second method comprises the following steps:
firstly, respectively adding chloroplatinic acid precursor solution and sodium hydroxide precursor solution with a molar ratio of 1:4-1:9 into a precursor solution tank, converging the solutions into a solution mixing device through a pump, feeding the solutions into a spiral pipeline, starting an ultrasonic device in the solution mixing device, and carrying out ultrasonic treatment on the precursor solution;
secondly, ultrasonically mixing the precursor solution in a solution mixing device, then feeding the precursor solution into a mixed solution tank, and starting a pump between the mixed solution tank and a charging bucket after all the precursor mixed solution enters the mixed solution tank;
thirdly, after the carbon carrier is added into the material tank, starting a pump to completely add the precursor mixed solution in the mixed solution tank into the material tank, and then starting the ultrasonic treatment of the solid material mixing device for 5-15 min;
fourthly, after the ultrasonic treatment is finished, starting the stirrer, and stirring at the rotating speed of 150 plus 250rpm for 20-50 min;
fifthly, drying and H processing the slurry after stirring2And (5) sintering, cleaning and drying in the reducing atmosphere of + Ar to obtain the carbon-supported platinum nano catalyst.
9. The method according to claim 8, wherein the ratio of the carbon carrier to the precursor mixed solution is 30 to 80g/L, and the volume of the chloroplatinic acid precursor solution is calculated according to the loading amount of Pt in the carbon-supported platinum nanocatalyst being 20 to 60%.
10. The method as claimed in claim 8, wherein the sintering temperature is 200 ℃ and 500 ℃ and the time is 0.5-4h, and the cleaning is performed by using an aqueous solution.
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