High-activity alkaline hydrogen evolution catalyst and preparation method thereof
Through the preparation of WOx-Pt3Ni/C catalyst, the problem of low hydrogen precipitation reaction activity in alkaline media was solved, and the efficient catalysis and industrial production were achieved, and the excellent performance in the electrolytic water of anion exchange membrane was demonstrated.
Patent Information
- Application Number
- CN202411429701.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-14
- Publication Date
- 2025-01-03
AI Technical Summary
The hydrogen precipitation reaction (HER) catalyst in existing alkaline media is low in activity, making it difficult to effectively catalyze water adsorption and dissociation in mild and weak alkaline environments, and there are challenges in the design and development of multifunctional site catalysts, especially in maintaining On the problem of uniformity of catalyst surface modification and particle size distribution.
Using WOx-Pt3Ni/C as a highly active alkaline hydrogen evolution catalyst, Pt3Ni is assisted by hexacarbonyl tungsten, and WOx is generated in situ on its surface. Combined with ultrasonic stirring of carbon support, a small particle size, uniform dispersion and high loading capacity are prepared. The catalyst simplifies the process and reduces the drying temperature.
It realizes efficient catalytic activity of hydrogen precipitation reaction, improves the production efficiency and stability of the catalyst, is easy to produce in industrialized production, and shows excellent performance in the electrolytic water of anion exchange membrane.
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Figure CN119243241A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of catalytic materials, and in particular relates to a high-activity alkaline hydrogen evolution catalyst and a preparation method thereof. Background Art
[0002] Hydrogen energy is abundant in resources and is green and low-carbon, and is an important part of the future energy system. Electrolysis of water to produce hydrogen combined with renewable energy to achieve zero-carbon "green hydrogen" production is an ideal way to produce hydrogen. Its development is crucial to building a clean, low-carbon, safe and efficient energy system, and it is necessary to accelerate the process of technology research and development and commercialization. Anion exchange membrane water electrolysis (AEMWE) hydrogen production is an emerging hydrogen production technology that combines the cost-effectiveness of alkaline water electrolysis (AEM) and the high efficiency of proton exchange membrane water electrolysis (PEMWE). The main advantage of AEMWE technology is that it can operate in a mild and weakly alkaline environment, broadening the selection range of catalysts and electrode materials, and reducing dependence on anode precious metals (such as iridium). However, the catalytic activity of the hydrogen evolution reaction of the benchmark platinum catalyst in an alkaline medium is 2 to 3 orders of magnitude lower than that in an acidic medium (HA Gasteiger et al., Energy Environ. Sci. 2014, 7, 2255-2260.). Because in alkaline media, active hydrogen intermediates (H*) are produced by breaking the strong covalent bonds of H2O molecules, which is different from the H3O in acidic media. + It is produced by reduction. Studies have shown that the adsorption energy of H2O (ΔE H2O ), H2O dissociation energy barrier (ΔG H2O ) and H adsorption free energy (ΔG H* ) plays a key role in enhancing the alkaline HER activity (S. Wei et al., Nat. Catal. 2019, 2, 134-141.). Single-site catalysts often find it difficult to break the constraints between the key intermediates of alkaline HER. Ideal alkaline HER catalysts need to be able to simultaneously enhance the catalyst's ability to adsorb and dissociate water and have a suitable H adsorption effect. Combining multiple active sites can change the local environment to accelerate the elementary steps, and it is expected to achieve high current density HER reactions. Platinum-based alloys (such as Pt-Ni and Pt-Co) can increase their alkaline properties to a certain extent through electronic effects and the creation of water adsorption sites. However, these methods still find it difficult to achieve a reduction in the activation barrier for water dissociation and OH ad The construction of multifunctional site catalysts also faces the difficulty of precisely controlling the reaction characteristics of each active site, and the design and development of efficient alkaline HER catalysts are still challenging.
[0003] The preparation methods of PtNi / C alloy catalysts mainly include oleic acid / oleylamine method (M.Shao et al.NanoLett.2017,17,3926-3931), DMF / benzoic acid liquid phase impregnation reduction method (Y.Huang et al.J.Am.Chem.Soc.2018,140,9046-9050) and multi-step gas phase reduction method (X.Sun et al.ACSCatal.2020,10,7,4205-4214). The preparation process of oleic acid / oleylamine method is simple and reproducible, but the temperature and cost of the synthesis process are high, and the adsorption of oleylamine on the surface of the obtained catalyst is difficult to remove, resulting in the coverage of catalytic active sites and reducing the catalytic efficiency; although the production process of impregnation reduction method is simple, the particle size distribution of the catalyst metal nanoparticles obtained by impregnation reduction method is wide and the dispersibility is poor; in the multi-step reduction method, the spontaneous nucleation during the reduction process of the second metal is introduced, resulting in the uneven modification of the catalyst surface. Summary of the invention
[0004] The object of the present invention is to provide a highly active alkaline hydrogen evolution catalyst and its preparation method and application. The alkaline hydrogen evolution catalyst has the advantages of small particle size, uniform dispersion and high loading amount. The preparation method is simple, environmentally friendly and easy to industrially scale up. The specific technical scheme of the present invention is as follows:
[0005] A highly active alkaline hydrogen evolution catalyst, the main active ingredient of which is WO x -Pt3Ni / C.
[0006] Preferably, WO x -The Pt content in Pt3Ni / C is 5wt%-60wt%.
[0007] A method for preparing the above-mentioned alkaline hydrogen evolution catalyst comprises the following steps:
[0008] (1) mixing a precursor, ferric chloride, hexadecyltrimethylammonium chloride, polyvinylpyrrolidone, hexacarbonyl tungsten and ethanol uniformly to obtain a reaction solution, then performing a solvothermal reaction at 160-200° C. for 2-8 hours, cooling to room temperature, sequentially separating and washing, and finally dispersing in ethanol to obtain a first dispersion;
[0009] (2) washing the first dispersion with acetic acid at 50-70° C. for 10 h, cooling it to room temperature, and obtaining a second dispersion by separation and washing;
[0010] (3) ultrasonically stirring the second dispersion and the carbon support for 2-12 hours, and then separating and drying to obtain an alkaline hydrogen evolution catalyst;
[0011] The precursor includes a platinum precursor and a nickel precursor in a mass ratio of 1:0.3-3, and the mass ratio of the precursor, ferric chloride, hexadecyltrimethylammonium chloride, polyvinylpyrrolidone, hexacarbonyl tungsten and carbon carrier is 1:1-6:1-5:1-5:1.5-2:0.5-4.
[0012] In the above preparation method, hexacarbonyl tungsten is first used to assist in the synthesis of Pt3Ni, and WO is in situ generated on the surface of Pt3Ni. x , to obtain WO x -First dispersion of Pt3Ni nanooctahedra, followed by removal of WO using acetic acid x -Pt3Ni nano-octahedral surface adsorbent, making it more hydrophilic, and finally adding carbon carrier ultrasonic mixing to obtain alkaline hydrogen evolution catalyst (WO x -Pt3Ni / C).
[0013] Preferably, the platinum precursor is platinum acetylacetonate.
[0014] More preferably, the nickel precursor is at least one of nickel acetylacetonate, nickel chloride hexahydrate, and nickel acetate.
[0015] Preferably, the molecular weight of polyvinylpyrrolidone is 55000 Da.
[0016] Preferably, the mass ratio of the precursor to the ethanol in the reaction solution is 1:1-100.
[0017] Preferably, the mass ratio of acetic acid to ethanol in the first dispersion is 1:1-5.
[0018] Preferably, the carbon carrier is one or more of carbon black, carbon nanotubes, activated carbon and biochar.
[0019] Preferably, the drying in step (3) is carried out under a vacuum atmosphere, the drying temperature is 40-80° C., and the drying time is 2-8 h.
[0020] The present invention has at least the following beneficial effects:
[0021] The present invention uses hexacarbonyl tungsten to assist in the synthesis of Pt3Ni, and in situ generates WO on the surface of Pt3Ni. x , get WO x -Pt3Ni / C is an alkaline hydrogen evolution catalyst with the main active ingredient. The synthesis of the catalyst is completed in one step, the operation is simple, the synthesis time is short, the production efficiency is improved, and it is easy to scale up the production; ethanol is used as a solvent, which is environmentally friendly; using a volatile organic solvent to wash the catalyst reduces the drying temperature, reduces the drying time, and is conducive to improving the stability of the catalyst. The WO prepared by the present invention x-Pt3Ni / C has the advantages of small particle size, uniform dispersion and high Pt loading and exhibits excellent catalytic activity in hydrogen evolution reaction (HER). BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 WO prepared in Example 1 and Comparative Example 1 of the present invention x - Transmission electron microscope (TEM) images of Pt3Ni nanooctahedron and Pt3Ni nanooctahedron, wherein (a) is Example 1 and (b) is Comparative Example 1;
[0023] Figure 2 This is Example 1 (WO x -Pt3Ni) and Comparative Example 1 (Pt3Ni) XRD comparison diagram;
[0024] Figure 3 This is Example 1 (WO x -Pt3Ni / C), Comparative Example 1 (Pt3Ni / C) and Comparative Example 2 (Pt / C) for alkaline hydrogen evolution performance comparison;
[0025] Figure 4 The alkaline hydrogen evolution catalyst (WO x -Pt3Ni / C) and comparative example 2 (Pt / C) anion exchange membrane water electrolysis performance test comparison chart. DETAILED DESCRIPTION
[0026] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is described in more detail below with reference to the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited to these embodiments.
[0027] Example 1
[0028] (1) 0.2 g of platinum acetylacetonate, 0.13 g of nickel chloride hexahydrate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, 0.5 g of polyvinylpyrrolidone and 0.5 g of tungsten hexacarbonyl were weighed and stirred for 30 min in air at room temperature using 60 mL of ethanol as solvent to obtain a uniform dispersion. The mixture was reacted at 180 °C for 3 h by solvothermal method, cooled to room temperature, separated and collected by acetone, washed with acetone and ethanol respectively, and then dispersed in 20 mL of ethanol to obtain a first dispersion (WO 2 x -Pt3Ni);
[0029] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:1) to the first dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second dispersion;
[0030] (3) Add 0.4 g of Cabot VXC-72 carbon black to the second dispersion, stir for 10 h after ultrasonication for 2 h until the mixture is uniformly mixed, separate and collect, and vacuum dry at 60 ° C to obtain a highly active alkaline hydrogen evolution catalyst (WO x -Pt3Ni / C), the Pt content of which is 20wt%.
[0031] Example 2
[0032] (1) Weigh 0.2 g of platinum acetylacetonate, 0.13 g of nickel chloride hexahydrate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, 0.5 g of polyvinylpyrrolidone and 0.5 g of tungsten hexacarbonyl, use 60 mL of ethanol as solvent, stir for 30 min in air at room temperature to obtain a uniform dispersion, react at 180 ° C for 6 h, cool to room temperature, separate and collect with acetone, wash with acetone and ethanol, and then disperse in 20 mL of ethanol to obtain a first dispersion (WO 2 x -Pt3Ni);
[0033] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:1) to the first dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second dispersion;
[0034] (3)To WO x 0.4 g of Cabot's VXC-72 carbon black was added to the Pt3Ni nano-octahedral ethanol dispersion, and the mixture was stirred for 10 h after ultrasonic treatment for 2 h until uniform mixing. The mixture was separated and collected, and vacuum dried at 60 °C to obtain a highly active alkaline hydrogen evolution catalyst (WO x -Pt3Ni / C), the Pt content of which is 20wt%.
[0035] Example 3
[0036] (1) 0.2 g of platinum acetylacetonate, 0.13 g of nickel chloride hexahydrate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, 0.5 g of polyvinylpyrrolidone and 0.5 g of tungsten hexacarbonyl were weighed and stirred for 30 min in air at room temperature using 60 mL of ethanol as a solvent to obtain a uniform dispersion. The mixture was reacted at 180 °C for 9 h by solvothermal method, cooled to room temperature, separated and collected by acetone, washed with acetone and ethanol, and then dispersed in 20 mL of ethanol to obtain a first dispersion (WO 2 x -Pt3Ni);
[0037] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:1) to the first dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second dispersion;
[0038] (3) Add 0.4 g of Cabot's VXC-72 conductive carbon black to the second dispersion, stir for 10 h after ultrasonic treatment for 2 h until the mixture is uniformly mixed, separate and collect, and vacuum dry at 60 ° C to obtain a highly active alkaline hydrogen evolution catalyst (WO x -Pt3Ni / C), the Pt content of which is 20wt%.
[0039] Example 4
[0040] (1) 0.2 g of platinum acetylacetonate, 0.13 g of nickel chloride hexahydrate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, 0.5 g of polyvinylpyrrolidone and 0.5 g of tungsten hexacarbonyl were weighed and stirred for 30 min in air at room temperature using 60 mL of ethanol as solvent to obtain a uniform dispersion. The mixture was reacted at 180 °C for 3 h by solvothermal method, cooled to room temperature, separated and collected by acetone, washed with acetone and ethanol, and then dispersed in 20 mL of ethanol to obtain a first dispersion (WO 2 x -Pt3Ni);
[0041] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:4) to the first dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second dispersion;
[0042] (3) Add 0.4 g of Cabot's VXC-72 conductive carbon black to the second dispersion, stir for 10 h after ultrasonic treatment for 2 h until the mixture is uniformly mixed, separate and collect, and vacuum dry at 60 ° C to obtain a highly active alkaline hydrogen evolution catalyst (WO x -Pt3Ni / C), the Pt content of which is 20wt%.
[0043] Example 5
[0044] (1) 0.2 g of platinum acetylacetonate, 0.13 g of nickel chloride hexahydrate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, 0.5 g of polyvinylpyrrolidone and 0.5 g of tungsten hexacarbonyl were weighed and stirred for 30 min in air at room temperature using 60 mL of ethanol as solvent to obtain a uniform dispersion. The mixture was reacted at 180 °C for 3 h by solvothermal method, cooled to room temperature, separated and collected by acetone, washed with acetone and ethanol, and then dispersed in 20 mL of ethanol to obtain a first dispersion (WO 2 x -Pt3Ni);
[0045] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:9) to the first dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second dispersion;
[0046] (3) Add 0.4 g of Cabot's VXC-72 conductive carbon black to the second dispersion, stir for 10 h after ultrasonic treatment for 2 h until the mixture is uniformly mixed, separate and collect, and vacuum dry at 60 ° C to obtain a highly active alkaline hydrogen evolution catalyst (WO x -Pt3Ni / C), the Pt content of which is 20wt%.
[0047] Example 6
[0048] (1) 0.2 g of platinum acetylacetonate, 0.15 g of nickel acetylacetonate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, 0.5 g of polyvinylpyrrolidone and 0.5 g of tungsten hexacarbonyl were weighed and stirred for 30 min in air at room temperature using 60 mL of ethanol as a solvent to obtain a uniform dispersion. The mixture was reacted at 180 °C for 3 h using a solvothermal method. After cooling to room temperature, the mixture was separated and collected using acetone, washed with acetone and ethanol, and then dispersed in 20 mL of ethanol to obtain a first dispersion (WO 3). x -Pt3Ni);
[0049] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:1) to the first dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second dispersion;
[0050] (3) Add 0.4 g of Cabot's VXC-72 conductive carbon black to the second dispersion, stir for 10 h after ultrasonic treatment for 2 h until the mixture is uniformly mixed, separate and collect, and vacuum dry at 60 ° C to obtain a highly active alkaline hydrogen evolution catalyst (WO x -Pt3Ni / C), the Pt content of which is 20wt%.
[0051] Example 7
[0052] (1) 0.2 g of acetylacetone, 0.09 g of nickel acetate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, 0.5 g of polyvinylpyrrolidone and 0.5 g of tungsten hexacarbonyl were weighed and stirred for 30 min in air at room temperature using 60 mL of ethanol as a solvent to obtain a uniform dispersion. The mixture was reacted at 180 °C for 3 h using a solvothermal method. After cooling to room temperature, the mixture was separated and collected using acetone, washed with acetone and ethanol, and then dispersed in 20 mL of ethanol to obtain a first dispersion (WO 2 x -Pt3Ni);
[0053] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:1) to the first dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second dispersion;
[0054] (3) Add 0.4 g of Cabot's VXC-72 conductive carbon black to the second dispersion, stir for 10 h after ultrasonic treatment for 2 h until the mixture is uniformly mixed, separate and collect, and vacuum dry at 60 ° C to obtain a highly active alkaline hydrogen evolution catalyst (WO x -Pt3Ni / VXC-72), the Pt content of which is 20wt%.
[0055] Example 8
[0056] (1) 0.2 g of platinum acetylacetonate, 0.09 g of nickel acetate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, 0.5 g of polyvinylpyrrolidone and 0.5 g of tungsten hexacarbonyl were weighed and stirred for 30 min in air at room temperature using 60 mL of ethanol as a solvent to obtain a uniform dispersion. The mixture was reacted at 180 °C for 3 h using a solvothermal method. After cooling to room temperature, the mixture was separated and collected using acetone, washed with acetone and ethanol, and then dispersed in 20 mL of ethanol to obtain a first dispersion (WO 2 x -Pt3Ni);
[0057] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:1) to the first dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second dispersion;
[0058] (3) 0.4 g of carbon nanotubes (CNT) was added to the second dispersion, and the mixture was ultrasonicated for 2 h and then stirred for 10 h until the mixture was uniformly mixed. The mixture was separated and collected, and vacuum dried at 60 °C to obtain a highly active alkaline hydrogen evolution catalyst (WO x -Pt3Ni / CNT), whose Pt content is 20wt%.
[0059] Example 9
[0060] (1) 0.2 g of platinum acetylacetonate, 0.13 g of nickel chloride hexahydrate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, 0.5 g of polyvinylpyrrolidone and 0.5 g of tungsten hexacarbonyl were weighed and stirred for 30 min in air at room temperature using 60 mL of ethanol as a solvent to obtain a uniform dispersion. The mixture was reacted at 180 °C for 3 h using a solvothermal method. After cooling to room temperature, the mixture was separated and collected using acetone, washed with acetone and ethanol, and then dispersed in 20 mL of ethanol to obtain a first dispersion (WO 2 x -Pt3Ni);
[0061] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:1) to the first dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second dispersion;
[0062] (3) Add 0.4 g of Ketjen black (KB) to the second dispersion, ultrasonicate for 2 h, stir for 10 h until the mixture is uniformly mixed, separate and collect, and vacuum dry at 60 °C to obtain a highly active alkaline hydrogen evolution catalyst (WO x -Pt3Ni / KB), the Pt content of which is 20wt%.
[0063] Example 10
[0064] (1) 0.2 g of platinum acetylacetonate, 0.13 g of nickel chloride hexahydrate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, 0.5 g of polyvinylpyrrolidone and 0.5 g of tungsten hexacarbonyl were weighed and stirred for 30 min in air at room temperature using 60 mL of ethanol as a solvent to obtain a uniform dispersion. The mixture was reacted at 180 °C for 3 h using a solvothermal method. After cooling to room temperature, the mixture was separated and collected using acetone, washed with acetone and ethanol, and then dispersed in 20 mL of ethanol to obtain a first dispersion (WO 2 x -Pt3Ni);
[0065] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:1) to the first dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second dispersion;
[0066] (3) Add 0.15 g of Cabot VXC-72 conductive carbon black to the second dispersion, stir for 10 h after ultrasonic treatment for 2 h until the mixture is uniformly mixed, separate and collect, and vacuum dry at 60 ° C to obtain a highly active alkaline hydrogen evolution catalyst (WO x -Pt3Ni / VXC-72), the Pt content of which is 40wt%.
[0067] Comparative Example 1
[0068] (1) Weigh 0.2 g of platinum acetylacetonate, 0.13 g of nickel chloride hexahydrate, 0.072 g of ferric chloride, 0.5 g of hexadecyltrimethylammonium chloride, and 0.5 g of polyvinylpyrrolidone, use 60 mL of ethanol as a solvent, stir for 30 min in air at room temperature to obtain a uniform dispersion, react at 180 ° C for 3 h by solvothermal method, cool to room temperature, separate and collect with acetone, wash with acetone and ethanol respectively, and then disperse in 20 mL of ethanol to obtain a first comparative dispersion (Pt3Ni);
[0069] (2) adding 20 mL of acetic acid (acetic acid: ethanol = 1:1) to the first comparative dispersion, acid-washing at 70° C. for 10 h, cooling to room temperature, separating and collecting with acetone, washing with acetone and ethanol, and then dispersing in 20 mL of ethanol to obtain a second comparative dispersion;
[0070] (3) Add 0.4 g of Cabot's VXC-72 carbon black to the second comparative dispersion, ultrasonicate for 2 h, and stir for 10 h until the mixture is uniformly mixed. The mixture is separated and collected, and vacuum dried at 60° C. to obtain a comparative catalyst (Pt3Ni / C) having a Pt content of 20 wt %.
[0071] Comparative Example 2
[0072] Comparative Example 2 is a 40 wt % JM catalyst (ie, Pt / C) produced by Johnson Matthey.
[0073] Performance Testing:
[0074] 1. Transmission electron microscopy images of the alkaline hydrogen evolution catalyst prepared in Example 1 and the comparative catalyst prepared in Comparative Example 1 are as follows: Figure 1 As shown, it can be seen that Example 1 is dispersed more uniformly on the carbon support.
[0075] 2. The second dispersion prepared in Example 1 and the comparative second dispersion prepared in Comparative Example 1 were separated and the solid phase was subjected to X-ray diffraction. The results are as follows: Figure 2 shown.
[0076] 3. The three-electrode system of rotating disk electrode (RDE) and AEMWE tests were performed on Example 1, Comparative Example 1 and Comparative Example 2. The specific test conditions are as follows:
[0077] (1) RDE test:
[0078] ① Electrocatalyst slurry preparation: Weigh an appropriate amount of Example 1, Comparative Example 1 or Comparative Example 2 and add it to a mixed solution (isopropanol: water: nafion mass ratio is 7.9:2:0.1), and disperse it evenly by ultrasonic at 20°C to obtain an electrocatalyst sauce, wherein the slurry preparation concentration is 0.5 mg Pt / mL.
[0079] ② The working electrode was a rotating disk glassy carbon electrode, the reference electrode was a Hg|HgO electrode, the counter electrode was a carbon rod, and the electrolyte solution was a 1 M KOH aqueous solution (pH = 14).
[0080] ③ The potential range is 0.05 to -0.4 (V vs. RHE), the scanning speed is: 50mV / s (CV), 10mV / s (RDE), and the rotation rate is: 1600rpm.
[0081] ④ Take 6 μL of catalyst slurry and drop it onto the working electrode (3 ug Pt ), wait for it to dry naturally and then test it. The results are as follows Figure 3 As shown, it can be seen that the alkaline hydrogen evolution catalyst (WO x -Pt3Ni / C) has better alkaline hydrogen evolution catalytic activity.
[0082] (2) AEMWE test:
[0083] In the case of a serpentine flow channel (effective area: 2×2cm 2 WO was tested in an anion exchange membrane water electrolyzer (AEMWE) x -Practical applications of Pt3Ni / C electrocatalysts.
[0084] Among them, stainless steel and titanium plates are used as cathode plates and anode plates respectively. AM01-80 (80 μm) anion exchange membrane was immersed in 1 M KOH solution overnight for activation before use. The electrocatalyst slurry prepared in Example 1, Comparative Example 1 or Comparative Example 2 was sprayed on one side of the anion exchange membrane using a spray gun, and the loading amount was about 1.0 mg / cm 2 , self-supporting NiFeOH x -NF (nickel foam) was used as the anode electrocatalyst and carbon paper (CP) was used as the cathode porous current collector to assemble NiFeOH x NF|| AM01-110||Electrocatalyst slurry||CP system was used for further testing.
[0085] The AEMWE test was performed at 80 °C, using a peristaltic pump to pump 1.0 M KOH at a flow rate of 30 mL / min. The polarization curve was tested by the step current method, with the current density increasing from 0.1 A / cm 2 Up to 4.0A / cm 2 , the results are as follows Figure 4 As shown, it can be seen that Example 1 can achieve a higher current density than Comparative Example 1 at the same potential, indicating that the alkaline hydrogen evolution catalyst prepared in Example 1 has a higher catalytic activity.
[0086] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some or all of the technical features thereof may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A highly active alkaline hydrogen evolution catalyst, characterized in that: Its main active ingredient is WO x -Pt3Ni / C.
2. The alkaline hydrogen evolution catalyst according to claim 1, characterized in that The WO x -The Pt content in Pt3Ni / C is 5wt%-60wt%.
3. A method for preparing the alkaline hydrogen evolution catalyst according to claim 1 or 2, characterized in that: The steps include: (1) mixing a precursor, ferric chloride, hexadecyltrimethylammonium chloride, polyvinylpyrrolidone, hexacarbonyl tungsten and ethanol uniformly to obtain a reaction solution, then performing a solvothermal reaction at 160-200° C. for 2-8 hours, cooling to room temperature, separating and washing in sequence, and finally dispersing in ethanol to obtain a first dispersion; (2) washing the first dispersion with acetic acid at 50-70° C. for 10 h, cooling it to room temperature, and obtaining a second dispersion by separation and washing; (3) ultrasonically stirring the second dispersion and the carbon support for 2-12 hours, and then separating and drying to obtain the alkaline hydrogen evolution catalyst; Wherein, the precursor comprises a platinum precursor and a nickel precursor in a mass ratio of 1:0.3-3, and the mass ratio of the precursor, the ferric chloride, the hexadecyltrimethylammonium chloride, the polyvinylpyrrolidone, the hexacarbonyl tungsten and the carbon carrier is 1:1-6:1-5:1-5:1-2:0.5-4.
4. The method for preparing the alkaline hydrogen evolution catalyst according to claim 3, wherein The platinum precursor is platinum acetylacetonate.
5. The method for preparing the alkaline hydrogen evolution catalyst according to claim 3 or 4, characterized in that: The nickel precursor is at least one of nickel acetylacetonate, nickel chloride hexahydrate, and nickel acetate.
6. The method for preparing the alkaline hydrogen evolution catalyst according to claim 3, characterized in that: The molecular weight of the polyvinyl pyrrolidone is 55 kDa.
7. The method for preparing the alkaline hydrogen evolution catalyst according to claim 3, characterized in that: The mass ratio of the precursor to the ethanol in the reaction solution is 1:1-100.
8. The method for preparing the alkaline hydrogen evolution catalyst according to claim 3, characterized in that: The mass ratio of the acetic acid to the ethanol in the first dispersion is 1:1-5.
9. The method for preparing the alkaline hydrogen evolution catalyst according to claim 3, characterized in that: The carbon carrier is one or more of carbon black, carbon nanotubes, activated carbon and biochar.
10. The method for preparing the alkaline hydrogen evolution catalyst according to claim 3, characterized in that: The drying in step (3) is carried out under a vacuum atmosphere, the drying temperature is 40-80° C., and the drying time is 2-8 hours.