A catalytic composite material, a preparation method and application thereof, and a catalytic electrode and application thereof
By loading PdxMy alloy nanoparticles onto a support, the problem of low electrolysis efficiency of palladium electrodes was solved, realizing a highly efficient coal slurry electrolysis hydrogen production process, reducing costs and making it suitable for industrial applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHENYANG INSTITUTE OF CHEMICAL TECHNOLOGY
- Filing Date
- 2022-12-09
- Publication Date
- 2026-04-21
AI Technical Summary
Existing palladium electrodes have low electrolysis efficiency in coal slurry electrolysis for hydrogen production, and pure platinum electrodes are expensive and have low reserves, making industrialization difficult.
A catalytic composite material, including a support and PdxMy alloy nanoparticles loaded on it, was prepared by combining transition metal elements with palladium to change the electronic structure of palladium. The resulting catalytic composite material was then used as an electrode material for coal slurry electrolysis to produce hydrogen, thereby improving the catalytic electrolysis efficiency.
It increases the current density of coal slurry electrolysis for hydrogen production, increases the contact area between the alloy catalyst and the electrolyte, reduces costs, and is suitable for industrial production.
Smart Images
Figure CN115821312B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of electrolytic hydrogen production technology, specifically relating to a catalytic composite material and its preparation method and application, and a catalytic electrode and its application. Background Technology
[0002] As an important secondary energy source, hydrogen is considered crucial in future energy strategies and is receiving increasing attention. Since Coughlin et al. published their findings in 1979, hydrogen production technology from coal slurry electrolysis has been extensively studied. Compared to water electrolysis, the theoretical electrolysis potential of coal slurry is 0.21V, significantly lower than the 1.23V of water electrolysis. The actual energy consumption of coal slurry electrolysis is approximately 50% of that of water electrolysis, demonstrating a clear energy-saving advantage. Compared to traditional coal gasification for hydrogen production, coal slurry electrolysis is conducted in an aqueous solution, where elements such as N and S in the coal are oxidized and dissolved in the solution, making it easier to process and preventing the production of NO. x It contains polluting gases such as SO2, thus having significant environmental advantages.
[0003] Currently, pure platinum electrodes are commonly used as anodes in coal slurry electrolysis for hydrogen production due to their excellent catalytic performance. However, pure platinum is expensive and scarce, making industrialization difficult. Palladium has similar chemical properties to platinum, and its abundant reserves and low price make it a popular alternative. However, existing palladium electrodes have relatively low electrolysis efficiency. Summary of the Invention
[0004] The purpose of this invention is to provide a catalytic composite material and its preparation method and application, as well as a catalytic electrode and its application. The catalytic composite material provided by this invention is used as an electrode material in coal slurry electrolysis for hydrogen production, and has high electrolysis efficiency.
[0005] To achieve the above objectives, the present invention provides the following technical solution:
[0006] This invention provides a catalytic composite material comprising a support and alloy nanoparticles loaded on the support, wherein the chemical composition of the alloy nanoparticles is Pd. x M y ;
[0007] M is a transition metal element;
[0008] The value of x ranges from 1 to 10, and the value of y ranges from 1 to 10.
[0009] Preferably, M includes one or more of Ni, Fe, Mo and Ti.
[0010] Preferably, the particle size of the alloy nanoparticles is 10–40 nm.
[0011] Preferably, the loading percentage of the alloy nanoparticles is 5% to 30%.
[0012] This invention also provides a method for preparing the catalytic composite material described in the above technical solution, comprising the following steps:
[0013] The support is impregnated in a solution containing palladium ions and M ions, and the impregnated support is subjected to a reduction reaction to obtain the catalytic composite material.
[0014] The molar ratio of Pd to M in the solution is 1:10 to 10:1.
[0015] Preferably, the method for preparing the solution containing palladium ions and M ions includes the following steps:
[0016] The palladium source, M source and water are mixed and subjected to ultrasonic treatment to obtain the solution containing palladium ions and M ions.
[0017] Preferably, the temperature of the reduction reaction is 300–1000°C, and the holding time is 1–5 hours.
[0018] The present invention also provides the application of the catalytic composite material described in the above technical solution or the catalytic composite material prepared by the preparation method described in the above technical solution in a catalytic electrode.
[0019] The present invention also provides a catalytic electrode, comprising an electrode substrate and an electrode material, wherein the electrode material is the catalytic composite material described in the above technical solution or the catalytic composite material prepared by the preparation method described in the above technical solution.
[0020] The present invention also provides the application of the catalytic electrode described in the above technical solution in the production of hydrogen by coal slurry electrolysis.
[0021] This invention provides a catalytic composite material comprising a support and alloy nanoparticles loaded on the support, wherein the chemical composition of the alloy nanoparticles is Pd. x M y M is a transition metal element; the value of x ranges from 1 to 10, and the value of y ranges from 1 to 10. In this invention, by combining a transition metal with a palladium alloy, the electronic structure of palladium can be changed, the binding energy of palladium can be reduced, and the catalytic composite material can be used as an electrode material in coal slurry electrolysis for hydrogen production, thereby further improving the catalytic electrolysis efficiency. Attached Figure Description
[0022] Figure 1 Here is a SEM image of the catalytic composite material obtained in Example 1;
[0023] Figure 2 XPS image of the catalytic composite material obtained in Example 1;
[0024] Figure 3 This is a TEM image of the catalytic composite material obtained in Example 1. Detailed Implementation
[0025] This invention provides a catalytic composite material comprising a support and alloy nanoparticles loaded on the support, wherein the chemical composition of the alloy nanoparticles is Pd. x M y ;
[0026] M is a transition metal element;
[0027] The value of x ranges from 1 to 10, and the value of y ranges from 1 to 10.
[0028] In this invention, M preferably includes one or more of Ni, Fe, Mo and Ti.
[0029] In this invention, the value of x ranges from 1 to 10, more preferably from 2 to 8, and even more preferably from 3 to 7. In this invention, the value of y ranges from 1 to 10, more preferably from 2 to 8, and even more preferably from 3 to 7.
[0030] In this invention, the particle size of the alloy nanoparticles is preferably 10-40 nm, and more preferably 20-30 nm.
[0031] In this invention, the carrier preferably includes one or more of carbon fiber, activated carbon, and carbon nanotubes.
[0032] In this invention, the loading percentage of the alloy nanoparticles is preferably 5% to 30%, more preferably 8% to 28%, and even more preferably 10% to 20%.
[0033] This invention also provides a method for preparing the catalytic composite material described in the above technical solution, comprising the following steps:
[0034] The support is impregnated in a solution containing palladium ions and M ions, and the impregnated support is subjected to a reduction reaction to obtain the catalytic composite material.
[0035] The molar ratio of Pd to M in the solution is 1:10 to 10:1.
[0036] In this invention, unless otherwise specified, all raw materials used in the preparation are commercially available products well known to those skilled in the art.
[0037] In this invention, the molar ratio of Pd to M in the solution is 1:10 to 10:1, more preferably 2:9 to 9:1, and even more preferably 3:8 to 8:1. In specific embodiments of this invention, the molar ratio of Pd to M is 1:1, 7:3, or 3:7.
[0038] In this invention, the method for preparing the solution containing palladium ions and M ions preferably includes the following steps:
[0039] The palladium source, M source and water are mixed and subjected to ultrasonic treatment to obtain the solution containing palladium ions and M ions.
[0040] In this invention, the palladium source preferably comprises one or more of chloropalladium acid, palladium chloride, and palladium nitrate. In this invention, the M source preferably comprises a soluble compound containing M. In this invention, the soluble compound containing M comprises a soluble metal salt containing M and / or a soluble oxide containing M. In this invention, the soluble metal salt containing M preferably comprises one or more of nickel nitrate, ferric nitrate, ammonium molybdate, and tetrabutyl titanate.
[0041] In this invention, the molar concentration of the palladium source in the mixed solution is preferably 1–500 mmol / L, more preferably 50–490 mmol / L, and even more preferably 100–480 mmol / L. In this invention, the molar concentration of the M source in the mixed solution is preferably 1–500 mmol / L, more preferably 50–490 mmol / L, and even more preferably 100–480 mmol / L.
[0042] The present invention does not impose any particular limitation on the mixing process; any process well known to those skilled in the art can be used. In the present invention, the ultrasonic treatment time is preferably 10 to 20 minutes.
[0043] In this invention, when the carrier is carbon fiber, it is preferable to pre-treat the carbon fiber before impregnation; the pre-treatment preferably includes: rinsing the carbon fiber with acetone and distilled water in sequence, drying and cooling to room temperature.
[0044] The present invention does not impose any particular limitation on the rinsing process; any process well-known to those skilled in the art can be used. In the present invention, the drying temperature is preferably 120°C, and the drying time is preferably 1 to 3 hours.
[0045] In this invention, the immersion time is preferably 4 to 6 hours. This invention does not impose any particular limitation on the immersion process, as long as the carrier is completely submerged in the solution.
[0046] Following the impregnation, the present invention preferably includes drying the impregnated carrier. In the present invention, the drying temperature is preferably 120°C, and the drying time is preferably 1–3 hours.
[0047] In this invention, the reduction reaction is preferably carried out in a mixed atmosphere of hydrogen and a protective gas; the volume ratio of hydrogen to protective gas in the mixed atmosphere is preferably 1:5. In this invention, the protective gas is preferably nitrogen. In this invention, the temperature of the reduction reaction is preferably 300–1000°C, more preferably 400–900°C, and even more preferably 500–800°C; the heating rate to the reduction reaction temperature is preferably 15°C / min; the holding time is preferably 1–5 h, more preferably 2–4 h, and even more preferably 2–3 h.
[0048] Following the reduction reaction, the present invention preferably further includes cooling the obtained material to room temperature. In the present invention, the cooling is preferably carried out in a protective gas atmosphere. In the present invention, the reduction reaction is preferably carried out in a tube furnace.
[0049] In a specific embodiment of the present invention, the reduction reaction process is preferably as follows:
[0050] The dried carrier is placed in a tube furnace, nitrogen is introduced to purge the air from the furnace, and the temperature is raised to the temperature required for the reduction reaction in a nitrogen atmosphere. Hydrogen is then introduced to carry out the reduction reaction.
[0051] This invention uses an impregnation reduction method to prepare catalytic composite materials, which is low in cost, simple to operate, and suitable for industrial production. It also enables alloy nanoparticles to be uniformly attached to the carrier, increasing the contact area between the alloy catalyst and the electrolyte and improving the electrolysis efficiency.
[0052] The present invention also provides the application of the catalytic composite material described in the above technical solution or the catalytic composite material prepared by the preparation method described in the above technical solution in a catalytic electrode.
[0053] The present invention also provides a catalytic electrode, comprising an electrode substrate and an electrode material, wherein the electrode material is the catalytic composite material described in the above technical solution or the catalytic composite material prepared by the preparation method described in the above technical solution.
[0054] This invention does not impose any particular limitation on the type of electrode substrate; any material well-known to those skilled in the art can be used. Similarly, this invention does not impose any particular limitation on the preparation method of the catalytic electrode; any process well-known to those skilled in the art can be used.
[0055] This invention also provides the application of the catalytic electrode described in the above technical solution in coal slurry electrolysis for hydrogen production. This invention does not impose any particular limitation on the implementation of the application; any process well-known to those skilled in the art can be used.
[0056] To further illustrate the present invention, the following detailed description, in conjunction with the accompanying drawings and embodiments, describes a catalytic composite material, its preparation method and application, and a catalytic electrode and its application, but these descriptions should not be construed as limiting the scope of protection of the present invention.
[0057] Example 1
[0058] The carbon fibers were rinsed with acetone and distilled water in sequence, and then dried in a drying oven at 120°C for 2 hours to obtain pretreated carbon fibers.
[0059] Mix 0.09 mmol palladium chloride, 0.09 mmol nickel nitrate and 8 mL deionized water (molar ratio of Pd to M is 1:1), and sonicate the mixture for 20 min to obtain the impregnation solution.
[0060] The pretreated carbon fibers were completely immersed in the impregnation solution obtained above for 4 hours. After being removed, they were placed in a drying oven and dried at 120°C for 2 hours. Then, they were placed in a tube furnace, and nitrogen was introduced to purge the air from the furnace. The temperature was increased to 450°C at a heating rate of 15°C / min in a nitrogen atmosphere. Hydrogen was introduced to carry out a reduction reaction for 2 hours, wherein the volume ratio of hydrogen to nitrogen was 1:5.
[0061] After the reduction reaction is completed, the mixture is cooled to room temperature in a nitrogen atmosphere to obtain the catalytic composite material (wherein the chemical composition of the supported alloy nanoparticles is PdNi, the particle size is 18 nm, and the loading percentage is 17%).
[0062] Example 2
[0063] The carbon fibers were rinsed with acetone and distilled water in sequence, and then dried in a drying oven at 120°C for 2 hours to obtain pretreated carbon fibers.
[0064] Mix 0.14 mmol palladium chloride, 0.06 mmol nickel nitrate and 8 mL deionized water (molar ratio of Pd to M is 7:3), and sonicate the mixture for 20 min to obtain the impregnation solution.
[0065] The pretreated carbon fibers were completely immersed in the impregnation solution obtained above for 4 hours. After being removed, they were placed in a drying oven and dried at 120°C for 2 hours. Then, they were placed in a tube furnace, and nitrogen was introduced to purge the air from the furnace. The temperature was increased to 450°C at a heating rate of 15°C / min in a nitrogen atmosphere. Hydrogen was introduced to carry out a reduction reaction for 2 hours, wherein the volume ratio of hydrogen to nitrogen was 1:5.
[0066] After the reduction reaction is completed, the mixture is cooled to room temperature in a nitrogen atmosphere to obtain the catalytic composite material (wherein the chemical composition of the supported alloy nanoparticles is Pd7Ni3, the particle size is 20 nm, and the loading percentage is 18%).
[0067] Example 3
[0068] The carbon fibers were rinsed with acetone and distilled water in sequence, and then dried in a drying oven at 120°C for 2 hours to obtain pretreated carbon fibers.
[0069] Mix 0.06 mmol palladium chloride, 0.14 mmol nickel nitrate and 8 mL deionized water (molar ratio of Pd to M is 3:7), and sonicate the mixture for 20 min to obtain the impregnation solution.
[0070] The pretreated carbon fibers were completely immersed in the impregnation solution obtained above for 4 hours. After being removed, they were placed in a drying oven and dried at 110°C for 2 hours. Then, they were placed in a tube furnace, and nitrogen was introduced to purge the air from the furnace. The temperature was increased to 450°C at a heating rate of 15°C / min in a nitrogen atmosphere. Hydrogen was introduced to carry out a reduction reaction for 2 hours, wherein the volume ratio of hydrogen to nitrogen was 1:5.
[0071] After the reduction reaction is complete, the mixture is cooled to room temperature in a nitrogen atmosphere to obtain the catalytic composite material (wherein the chemical composition of the supported alloy nanoparticles is Pd3Ni7, the particle size is 29 nm, and the loading percentage is 15%).
[0072] Comparative Example 1
[0073] The carbon fibers were rinsed with acetone and distilled water in sequence, and then dried in a drying oven at 120°C for 2 hours to obtain pretreated carbon fibers.
[0074] Mix 0.23 mmol palladium chloride with 8 mL deionized water, and sonicate the mixture for 20 min to obtain the impregnation solution.
[0075] The pretreated carbon fibers were completely immersed in the impregnation solution obtained above for 4 hours. After being removed, they were placed in a drying oven and dried at 110°C for 2 hours. Then, they were placed in a tube furnace, and nitrogen was introduced to purge the air from the furnace. The temperature was increased to 450°C at a heating rate of 15°C / min in a nitrogen atmosphere. Hydrogen was introduced to carry out a reduction reaction for 2 hours, wherein the volume ratio of hydrogen to nitrogen was 1:5.
[0076] After the reduction reaction is complete, the mixture is cooled to room temperature in a nitrogen atmosphere to obtain the catalytic composite material (wherein the chemical composition of the supported nanoparticles is Pd, the particle size is 29 nm, and the loading percentage is 20%).
[0077] Performance testing
[0078] Test Example 1
[0079] The catalytic composite material obtained in Example 1 was subjected to scanning electron microscopy (SEM) testing, and the resulting SEM images are shown below. Figure 1 As shown, from Figure 1 It can be seen that the alloy nanoparticles are uniformly loaded on the carbon fiber.
[0080] Test Example 2
[0081] The catalytic composite material obtained in Example 1 was subjected to X-ray photoelectron spectroscopy (XPS) analysis, and the resulting XPS pattern is shown below. Figure 2 As shown, from Figure 2 It can be seen that, compared with pure Pd, the binding energy of the catalytic composite material obtained in this invention shifts in the positive direction, indicating that a PdNi alloy is formed.
[0082] Test Example 3
[0083] The catalytic composite material obtained in Example 1 was subjected to transmission electron microscopy (TEM) testing, and the TEM images are shown below. Figure 3 As shown, from Figure 3 It can be seen that the catalytic composite material obtained by this invention is loaded with nanoscale alloy particles.
[0084] Test Example 4
[0085] The catalytic composite materials obtained in Examples 1-3 and Comparative Example 1 were tested for hydrogen production via coal slurry electrolysis.
[0086] The testing process is as follows:
[0087] 4.8g of coal powder was dissolved in 120mL of 1mol / L sulfuric acid to prepare a coal slurry solution with a concentration of 0.04g / mL as the anode solution (containing 1mol / L H2SO4, 0.04mol / L ferric sulfate and ferrous sulfate), and the cathode solution was a 1mol / L sulfuric acid solution.
[0088] The electrolysis apparatus used was an H-type electrolytic cell. The catalytic composite material obtained in Examples 1-3 and Comparative Example 1 was used as the electrode material, and a titanium mesh (1cm*1cm) was used as the electrode substrate to prepare the anode. Pt sheet electrodes were used as the cathode. The electrolytic cell was placed in a water bath and kept at a constant temperature of 80°C. The voltage was increased from 0V to 1.1V to produce hydrogen by electrolysis. The test results are shown in Table 1, where the current density is the current density at a voltage of 1.1V.
[0089] Table 1. Catalytic electrolysis results of the catalytic composite materials obtained in Examples 1-3 and Comparative Example 1.
[0090] <![CDATA[Current density (mA / cm 2 )]]> Example 1 73.43 Example 2 70.83 Example 3 61.92 Comparative Example 1 59.17
[0091] As can be seen from Table 1, compared with palladium loaded solely on carbon fiber in Comparative Example 1, the catalytic electrode prepared by the catalytic composite material provided by the present invention as an electrode material has a higher current density in coal slurry electrolysis for hydrogen production than that in Comparative Example 1. This indicates that the electrocatalytic activity of the catalytic composite material provided by the present invention in coal slurry electrolysis for hydrogen production is superior to that of pure palladium.
[0092] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.
Claims
1. A method for preparing a catalytic composite material, characterized in that, The steps are as follows; The carbon fibers were rinsed with acetone and distilled water in sequence, and then dried in a drying oven at 120°C for 2 hours to obtain pretreated carbon fibers. Mix 0.09 mmol palladium chloride, 0.09 mmol nickel nitrate and 8 mL deionized water, with a molar ratio of Pd to Ni of 1:
1. The resulting mixture is ultrasonically vibrated for 20 min to obtain the impregnation solution. The pretreated carbon fibers were completely immersed in the impregnation solution obtained above for 4 hours. After being removed, they were placed in a drying oven and dried at 120°C for 2 hours. Then, they were placed in a tube furnace, and nitrogen was introduced to purge the air from the furnace. The temperature was increased to 450°C at a heating rate of 15°C / min in a nitrogen atmosphere. Hydrogen was introduced to carry out a reduction reaction for 2 hours, wherein the volume ratio of hydrogen to nitrogen was 1:
5. After the reduction reaction is completed, the mixture is cooled to room temperature in a nitrogen atmosphere to obtain the catalytic composite material. The alloy nanoparticles supported on the catalytic composite material have a chemical composition of PdNi, a particle size of 18 nm, and a loading percentage of 17%.