Preparation method of ultra-high-performance electrolyzed water cathode supported platinum-carbon catalyst

Abstract

The invention provides a preparation method of a supported platinum-carbon nanomaterial, which comprises the following steps: firstly, mixing a platinum source, a carbon source and a solvent to obtain a precursor mixed solution; drying and grinding the precursor mixed solution obtained in the previous step to obtain powder; and finally, annealing the powder obtained in the previous step in a protective atmosphere and / or a reducing atmosphere to obtain the supported platinum-carbon nano material. The synthesis method is simple, the yield is high, the preparation process is green, pollution-free and environment-friendly, and the obtained catalyst Pt is small in particle size and is highly uniformly dispersed on a carbon carrier, so that the catalyst Pt has very high active site density, shows excellent catalytic activity in the water electrolysis process, is far higher than commercial Pt / C, and has good application prospects. And a new possibility is provided for large-scale production of the cathode catalyst through water electrolysis hydrogen production, and the method has a wide application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of electrolyzed water cathode catalysts, and relates to a preparation method and application of a supported platinum-carbon nanomaterial, and particularly relates to a preparation method of a super-high-performance electrolyzed water cathode supported platinum-carbon catalyst. Background Art

[0002] With the growth of the population, the demand for energy by humans is increasing day by day. However, traditional energy sources, including coal, oil, and natural gas, are all non-renewable once consumed. Therefore, there is an urgent need to reduce the dependence on traditional energy sources and accelerate the development of clean energy. Hydrogen, as a clean energy source, is known for its renewability and high calorific value and is considered an important intermediate energy carrier. However, the currently extracted "gray hydrogen" from fossil fuels still accounts for a large proportion. Ion exchange membrane electrolyzed water has great application prospects in the hydrogen energy market due to its good coupling with renewable energy, fast equipment start-stop speed, small floor area, low operation and maintenance costs, and high-efficiency production of high-purity hydrogen.

[0003] Due to the excellent HER activity of Pt-based materials, Pt / C is the most commonly used commercial catalyst at present, in which Pt is dispersed in the form of nanoparticles on a conductive and corrosion-resistant carrier. However, in practical applications, the migration or aggregation of Pt particles on the carrier, or the dissolution of Pt particles in the electrolyte, or the detachment of Pt particles due to the corrosion of the carbon carrier will all lead to a decrease in the catalyst activity.

[0004] Therefore, how to develop a more suitable supported platinum-carbon nanomaterial to solve the above problems existing in the prior art has become one of the focuses widely concerned by many front-line researchers in the industry. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a preparation method and application of a supported platinum-carbon nanomaterial, especially a preparation method of a super-high-performance electrolyzed water cathode supported platinum-carbon catalyst. In the catalyst synthesized by the preparation method provided by the present invention, the Pt particle size is small and evenly dispersed on the carrier, and it has more excellent catalyst activity compared with the commercial Pt / C catalyst, and has broad application prospects; moreover, the preparation method is simple, the conditions are mild, the operability is strong, the stability is good, and it is more suitable for the popularization and application of industrial production.

[0006] The present invention provides a preparation method of a supported platinum-carbon nanomaterial, comprising the following steps:

[0007] 1) Mix a platinum source, a carbon source, and a solvent to obtain a precursor mixed solution;

[0008] 2) Dry and grind the precursor mixed solution obtained in the above step to obtain a powder;

[0009] 3) Under a protective atmosphere and / or a reducing atmosphere, anneal the powder obtained in the above steps to obtain the supported platinum-carbon nanomaterial.

[0010] Preferably, the platinum source is one or more of chloroplatinic acid, potassium chloroplatinate, platinum trichloride, and platinum acetylacetonate;

[0011] The carbon source is carbon black;

[0012] The solvent is one or more of methanol, ethanol, acetone, and water.

[0013] Preferably, the mixing method includes ultrasonic treatment;

[0014] The power of the ultrasonic treatment is 30 - 80 W;

[0015] The time of the ultrasonic treatment is 15 - 60 min.

[0016] Preferably, the mixing temperature is 5 - 50 °C;

[0017] The drying temperature is 60 - 100 °C;

[0018] The drying time is 5 - 12 h.

[0019] Preferably, the protective atmosphere includes inert gas and / or nitrogen;

[0020] The reducing atmosphere includes hydrogen.

[0021] Preferably, the heating rate of the annealing is 5 - 10 °C / min;

[0022] The annealing temperature is 100 - 500 °C;

[0023] The annealing time is 1 - 3 h.

[0024] Preferably, in the supported platinum-carbon nanomaterial, the particle size of the Pt nanoparticles is 0.5 - 2 nm;

[0025] In the supported platinum-carbon nanomaterial, the loading amount of the Pt nanoparticles is 5% - 50%;

[0026] The supported platinum-carbon nanomaterial is specifically a cathode-supported platinum-carbon catalyst.

[0027] Preferably, the supported platinum-carbon nanomaterial is specifically an electrolyzed water cathode-supported platinum-carbon catalyst;

[0028] The electrolyzed water cathode-supported platinum-carbon catalyst is specifically a cathode-supported platinum-carbon catalyst in the hydrogen evolution reaction of electrolyzed water;

[0029] The cathode-supported platinum-carbon catalyst includes a catalyst for AEM electrolysis devices.

[0030] The present invention also provides an application of the supported platinum-carbon nanomaterial prepared by the preparation method according to any one of the above technical solutions in the field of catalysts.

[0031] Preferably, the catalyst is specifically a catalyst for the hydrogen evolution reaction in water electrolysis;

[0032] The oxygen evolution reaction is specifically the hydrogen evolution reaction at the cathode;

[0033] The application includes an application on an AEM electrolysis device.

[0034] The present invention provides a method for preparing a supported platinum-carbon nanomaterial, which includes the following steps: First, a platinum source, a carbon source, and a solvent are mixed to obtain a precursor mixed solution; then, the precursor mixed solution obtained in the above step is dried and ground to obtain a powder; finally, in a protective atmosphere and / or a reducing atmosphere, the powder obtained in the above step is annealed to obtain a supported platinum-carbon nanomaterial. Compared with the prior art, the present invention believes that the regulation of the Pt structure to increase its dispersion on the carrier, thereby increasing the specific surface area, is of great significance for developing efficient catalysts.

[0035] Based on this, the present invention creatively designs a preparation method for a super-high-performance alkaline water electrolysis cathode-supported platinum-carbon catalyst with a specific preparation route. This synthesis method is simple, has a high yield, the preparation process is green and pollution-free, and is environmentally friendly. The obtained catalyst has a small Pt particle size and is highly uniformly dispersed on the carbon carrier, so it has a high density of active sites and exhibits excellent catalytic activity during the water electrolysis process.

[0036] Moreover, the present invention can also control the reaction conditions to regulate the morphology and structure of the product, thereby optimizing the catalytic performance of the platinum-carbon catalyst. The performance of the obtained catalyst is much higher than that of commercial Pt / C, has better catalytic activity, provides a new possibility for the large-scale production of cathode catalysts for water electrolysis to produce hydrogen, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is a high-angle annular dark-field scanning transmission image of the platinum-carbon catalyst prepared in Examples 1-5 of the present invention;

[0038] Figure 2 It is an XRD pattern of the platinum-carbon catalyst prepared in Examples 1-5 of the present invention;

[0039] Figure 3 It is a performance graph of the catalyst prepared in Examples 1-5 of the present invention for an AEM electrolysis device;

[0040] Figure 4 Performance diagram of the catalyst prepared in Example 1 of the present invention and the commercial platinum-carbon catalyst for AEM electrolysis devices. Detailed implementation manners

[0041] To further understand the present invention, the preferred implementation manners of the present invention will be described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention rather than limiting the claims of the present invention.

[0042] For all raw materials of the present invention, there is no particular limitation on their sources, and they can be purchased on the market or prepared according to conventional methods well-known to those skilled in the art.

[0043] For the raw materials used in the present invention, there is no particular limitation on their purity, and it is preferably to use analytically pure or the purity requirements of the raw materials for preparing electrolytic water cathode catalyst materials well-known to those skilled in the art.

[0044] The present invention provides a preparation method of a supported platinum-carbon nanomaterial, comprising the following steps:

[0045] 1) Mix a platinum source, a carbon source and a solvent to obtain a precursor mixed solution;

[0046] 2) Dry and grind the precursor mixed solution obtained in the above step to obtain a powder;

[0047] 3) Anneal the powder obtained in the above step under a protective atmosphere and / or a reducing atmosphere to obtain a supported platinum-carbon nanomaterial.

[0048] The present invention first mixes a platinum source, a carbon source and a solvent to obtain a precursor mixed solution.

[0049] In the present invention, the platinum source is preferably one or more of chloroplatinic acid, potassium chloroplatinate, platinum trichloride and platinum acetylacetonate, and more preferably chloroplatinic acid, potassium chloroplatinate, platinum trichloride or platinum acetylacetonate.

[0050] In the present invention, the carbon source is preferably carbon black.

[0051] In the present invention, the solvent is preferably one or more of methanol, ethanol, acetone and water, and more preferably methanol, ethanol, acetone or water.

[0052] In the present invention, the mixing method preferably includes ultrasonic treatment.

[0053] In the present invention, the power of the ultrasonic treatment is preferably 30-80 W, more preferably 40-70 W, and even more preferably 50-60 W.

[0054] In the present invention, the time of the ultrasonic treatment is preferably 15 to 60 min, more preferably 20 to 55 min, still more preferably 25 to 50 min, still more preferably 30 to 45 min, and still more preferably 35 to 40 min.

[0055] In the present invention, the temperature of the mixing is preferably 5 to 50 °C, more preferably 15 to 40 °C, and still more preferably 25 to 30 °C.

[0056] In the present invention, the precursor mixed solution obtained in the above steps is dried and ground to obtain a powder.

[0057] In the present invention, the temperature of the drying is preferably 60 to 100 °C, more preferably 65 to 95 °C, still more preferably 70 to 90 °C, and still more preferably 75 to 85 °C.

[0058] In the present invention, the time of the drying is preferably 5 to 12 h, more preferably 6.5 to 10.5 h, and still more preferably 8 to 9 h.

[0059] Finally, in the present invention, under a protective atmosphere and / or a reducing atmosphere, the powder obtained in the above steps is annealed to obtain a supported platinum-carbon nanomaterial.

[0060] In the present invention, the protective atmosphere preferably includes an inert gas and / or nitrogen, and more preferably an inert gas or nitrogen.

[0061] In the present invention, the reducing atmosphere preferably includes hydrogen.

[0062] In the present invention, the heating rate of the annealing is preferably 5 to 10 °C / min, more preferably 5 to 9 °C / min, still more preferably 5 to 7 °C / min, and specifically can be 5 °C / min.

[0063] In the present invention, the temperature of the annealing is preferably 100 to 500 °C, more preferably 150 to 450 °C, still more preferably 200 to 400 °C, and still more preferably 250 to 350 °C.

[0064] In the present invention, the time of the annealing is preferably 1 to 3 h, more preferably 1.4 to 2.6 h, and still more preferably 1.8 to 2.2 h.

[0065] In the present invention, in the supported platinum-carbon nanomaterial, the particle size of the Pt nanoparticles is preferably 0.5 to 2 nm, more preferably 0.8 to 1.7 nm, and still more preferably 1.1 to 1.4 nm. In the present invention, the particle size of the Pt nanoparticles can reflect the degree of highly uniform dispersion of the Pt nanoparticles on the carrier, and the smaller the particle size, the better the dispersion degree.

[0066] In the present invention, in the supported platinum-carbon nanomaterial, the loading amount of Pt nanoparticles is preferably 5% to 50%, more preferably 15% to 40%, and even more preferably 25% to 30%.

[0067] In the present invention, the supported platinum-carbon nanomaterial is specifically preferably a cathode-supported platinum-carbon catalyst.

[0068] In the present invention, the supported platinum-carbon nanomaterial is specifically preferably an electrolyzed water cathode-supported platinum-carbon catalyst.

[0069] In the present invention, the electrolyzed water cathode-supported platinum-carbon catalyst is specifically preferably a cathode-supported platinum-carbon catalyst in the hydrogen evolution reaction of electrolyzed water.

[0070] In the present invention, the cathode-supported platinum-carbon catalyst preferably includes a catalyst for AEM electrolysis devices.

[0071] The present invention provides the application of the supported platinum-carbon nanomaterial prepared by the preparation method according to any one of the above technical solutions in the aspect of a catalyst.

[0072] In the present invention, the catalyst is specifically preferably a catalyst in the hydrogen evolution reaction of electrolyzed water.

[0073] In the present invention, the oxygen evolution reaction is specifically preferably a cathode hydrogen evolution reaction.

[0074] In the present invention, the application preferably includes the application on an AEM electrolysis device.

[0075] In order to complete and refine the overall technical solution of the present invention, better ensure the specific structure and morphology of the supported platinum-carbon nanomaterial, and further improve the performance of the supported platinum-carbon nanomaterial in alkaline electrolyzed water cathode hydrogen production and industrial AEM devices, the preparation method and application of the above ultra-high performance electrolyzed water cathode-supported platinum-carbon catalyst may specifically include the following content:

[0076] A preparation method of an electrolyzed water cathode-supported platinum-carbon catalyst includes the following steps:

[0077] (1) Add a platinum source and a carbon source to a solvent and ultrasonically disperse them evenly to obtain a precursor mixed solution.

[0078] (2) Transfer the precursor mixed solution to an evaporating dish and place it in an oven for drying.

[0079] (3) Grind the powder obtained by drying evenly and perform annealing treatment under a certain atmosphere.

[0080] Specifically, the ultrasonic power is 30 to 80 W; the ultrasonic time is 15 to 60 min; the reaction temperature is 5 to 50 °C.

[0081] Specifically, the platinum source is selected from one or more of chloroplatinic acid, potassium chloroplatinate, platinum trichloride, and platinum acetylacetonate.

[0082] Specifically, the selected carbon source is selected from one or more of XC72, KJ300, and KJ600.

[0083] Specifically, the solvent is one or more of methanol, ethanol, acetone, and ultrapure water.

[0084] Specifically, the specification of the evaporating dish is 9 cm.

[0085] Specifically, the drying temperature is 60 - 100 °C; the drying time is 5 - 12 h.

[0086] Specifically, the grinding time is 30 min.

[0087] Specifically, the atmosphere selected for the annealing treatment is one or more of Ar, N2, and H2.

[0088] Specifically, the heating rate is 5 °C / min, and the annealing temperature is 100 - 500 °C.

[0089] Specifically, the reaction further includes: centrifuging and separating the product after the reaction, and vacuum drying it after washing it multiple times with acetone, deionized water, and absolute ethanol.

[0090] The present invention also provides the application of the platinum-carbon nanomaterial prepared by the preparation method described in any one of the above technical solutions as a catalyst in the electrolytic water hydrogen evolution reaction.

[0091] Furthermore, the present invention provides the following preferred technical solutions:

[0092] Preferably, the platinum source and the carbon source (including chloroplatinic acid, potassium chloroplatinate, platinum trichloride, platinum acetylacetonate, XC72, KJ300, KJ600, etc.) are added to the solvent and dissolved, and ultrasonic dispersion is performed until it is uniformly dispersed to obtain a dissolved solution. The solvent is one or more of methanol, ethanol, acetone, and ultrapure water.

[0093] Preferably, the proportion of the platinum source is 5% - 50%, and the platinum content is fixed.

[0094] Preferably, the dissolved solution is transferred to an evaporating dish and placed in an oven until the solvent is completely removed.

[0095] Preferably, the drying temperature is 60 - 100 °C; the drying time is 5 - 12 h.

[0096] Preferably, the atmosphere selected for the annealing treatment is one or more of Ar, N2, and H2; the heating rate is 5 °C / min, and the annealing temperature is 100 - 500 °C.

[0097] Preferably, the reaction further includes: centrifuging, washing, and drying in an oven the product after the reaction.

[0098] The present invention also provides the application of the Pt / C nanomaterial prepared by the described preparation method as a catalyst in the cathode reaction of electrolytic water and industrial AEM devices.

[0099] The above content of the present invention provides a preparation method of a super-high-performance electrolytic water cathode-supported platinum-carbon catalyst and its application as a catalyst for the hydrogen evolution reaction in alkaline electrolytic water. The preparation method of the super-high-performance alkaline electrolytic water cathode-supported platinum-carbon catalyst with a specific preparation route provided by the present invention has a simple synthesis method, high yield, a green and pollution-free preparation process, is environmentally friendly, and the obtained catalyst has small Pt particle size and is highly uniformly dispersed on the carbon support, so it has a very high density of active sites and exhibits excellent catalytic activity during the electrolytic water process.

[0100] Moreover, the present invention can also regulate the morphology and structure of the product by controlling the reaction conditions, thereby optimizing the catalytic performance of the platinum-carbon catalyst. The performance of the obtained catalyst is far higher than that of commercial Pt / C, has better catalytic activity, provides a new possibility for the large-scale production of cathode catalysts for electrolytic water hydrogen production, and has broad application prospects.

[0101] To further illustrate the present invention, the following describes in detail a preparation method and application of a supported platinum-carbon nanomaterial provided by the present invention in combination with examples. However, it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed implementation methods and specific operation processes are given, only to further illustrate the features and advantages of the present invention, rather than a limitation on the claims of the present invention. The protection scope of the present invention is not limited to the following examples.

[0102] Example 1

[0103] Preparation of the platinum-carbon catalyst nanomaterial:

[0104] Dissolve 92 mg of platinum acetylacetonate and 180 mg of KJ 300 in 15 mL of acetone, and ultrasonically disperse for 30 min to obtain solution A; transfer solution A to a 9-cm evaporating dish, place it in an oven and dry at 80 °C for 8 h, grind the dried solid for 30 min to obtain black powder B; place black powder B in a ceramic boat, and then place it in a tube furnace. First, pre-pass a 3% H2 / Ar mixed gas for 20 min to remove the air in the tube. Subsequently, continue to pass the above mixed gas, and heat it to 250 °C at a heating rate of 5 °C / min. Anneal at this temperature for 1 h to fully reduce metal ions into metal nanoparticles. After the firing is completed, cool for 1 h to room temperature, collect the product, centrifuge, wash, and dry in an oven;

[0105] See Figure 1 , Figure 1 which is the high-angle annular dark-field scanning transmission electron microscopy image of the Pt / C catalysts prepared in Examples 1-5 of the present invention.

[0106] The highly dispersed Pt particles can be determined by Figure 1 the HRTEM images.

[0107] Example 2

[0108] Adjust the proportion of Pt in Example 1 from 20% to 5%, and keep other methods and conditions the same as those in Example 1.

[0109] Example 3

[0110] Adjust the proportion of Pt in Example 1 from 20% to 10%, and keep other methods and conditions the same as those in Example 1.

[0111] Example 4

[0112] Adjust the proportion of Pt in Example 1 from 20% to 30%, and keep other methods and conditions the same as those in Example 1.

[0113] Example 5

[0114] Adjust the proportion of Pt in Example 1 from 20% to 50%, and keep other methods and conditions the same as those in Example 1.

[0115] See Figure 2 , Figure 2 which is the XRD pattern of the Pt / C catalysts prepared in Examples 1-5 of the present invention.

[0116] The crystal structures of the above-prepared catalyst materials are all face-centered cubic structures of platinum, which can be determined by Figure 2 the XRD spectra.

[0117] Membrane electrode preparation and assembly:

[0118] The AEM electrolyzer device uses a two-electrode test. 30 mg of the active material is ball-milled for 20 min and then dispersed in a mixed solution of 1 mL of water, 3 mL of isopropanol, and 18 mg of PTFE, and ultrasonically treated for 30 min to obtain a uniformly dispersed catalyst slurry. The slurry is sprayed onto an anion exchange membrane with a thickness of 40 μm and an effective area of 2 cm × 2 cm, and the loading is 1 mg / cm 2 . The anode is NiFe-LDH@NF synthesized by the hydrothermal method. The anode porous transport layer is nickel foam, the cathode porous transport layer is hydrophilic carbon paper, and the flow channel is a serpentine flow channel, and an AEM device is assembled.

[0119] See Figure 3 , Figure 3Performance diagram of the catalysts prepared in Examples 1 to 5 of the present invention used in AEM electrolysis devices.

[0120] The results show that when the Pt content is 20%, the Pt particles are more evenly dispersed and have the best catalytic performance.

[0121] See also Figure 4 , Figure 4 Performance diagram of the catalyst prepared in Example 1 of the present invention and a commercial platinum-carbon catalyst used in an AEM electrolysis device.

[0122] The results show that compared with commercial catalysts, the catalyst prepared in Example 1 has better performance and has the potential for commercial application.

[0123] In summary, the platinum-carbon catalyst prepared in the present invention exhibits excellent catalytic performance in the AEM test.

[0124] The above is a detailed introduction to the preparation method of an ultra-high performance water electrolysis cathode supported platinum carbon catalyst provided by the present invention. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enables any technician in the field to practice the present invention, including the manufacture and use of any device or system, and the implementation of any combined method. It should be pointed out that for ordinary technicians in the field of this technology, without departing from the principles of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements that are not different from the textual expression of the claims, or if they include equivalent structural elements that are not substantially different from the textual expression of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A preparation method of a supported platinum-carbon nanomaterial, characterized in that, It includes the following steps: 1) After mixing a platinum source, a carbon source and a solvent, a precursor mixed solution is obtained; 2) After drying and grinding the precursor mixed solution obtained in the above step, a powder is obtained; 3) Under a protective atmosphere and / or a reducing atmosphere, the powder obtained in the above step is annealed to obtain a supported platinum-carbon nanomaterial.

2. The preparation method according to claim 1, wherein The platinum source is one or more of chloroplatinic acid, potassium chloroplatinate, platinum trichloride and platinum acetylacetonate; The carbon source is carbon black; The solvent is one or more of methanol, ethanol, acetone and water.

3. The preparation method according to claim 1, wherein, The mixing method includes ultrasonic treatment; The power of the ultrasonic treatment is 30 - 80 W; The time of the ultrasonic treatment is 15 - 60 min.

4. The preparation method according to claim 1, wherein The temperature of the mixing is 5 - 50 °C; The temperature of the drying is 60 - 100 °C; The time of the drying is 5 - 12 h.

5. The preparation method according to claim 1, wherein, The protective atmosphere includes an inert gas and / or nitrogen; The reducing atmosphere includes hydrogen.

6. The preparation method according to claim 1, characterized in that, The heating rate of the annealing is 5 - 10 °C / min; The temperature of the annealing is 100 - 500 °C; The time of the annealing is 1 - 3 h.

7. The preparation method according to claim 1, characterized in that, In the supported platinum-carbon nanomaterial, the particle size of the Pt nanoparticles is 0.5 - 2 nm; In the supported platinum-carbon nanomaterial, the loading amount of the Pt nanoparticles is 5% - 50%; The supported platinum-carbon nanomaterial is specifically a cathode-supported platinum-carbon catalyst.

8. The preparation method according to claim 1, wherein, The supported platinum-carbon nanomaterial is specifically an electrolyzed water cathode-supported platinum-carbon catalyst; The electrolyzed water cathode-supported platinum-carbon catalyst is specifically a cathode-supported platinum-carbon catalyst in the hydrogen evolution reaction of electrolyzed water; The cathode-supported platinum-carbon catalyst includes a catalyst for an AEM electrolysis device.

9. Application of the supported platinum-carbon nanomaterial prepared by the preparation method according to any one of claims 1 - 8 in terms of a catalyst.

10. The application according to claim 9, characterized in that, The catalyst is specifically a catalyst in the hydrogen evolution reaction of electrolyzed water; The oxygen evolution reaction is specifically a cathode hydrogen evolution reaction; The application includes an application on an AEM electrolysis device.

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