Ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst, preparation method and application thereof
By preparing ruthenium single-atom catalysts supported on ultrafine high-entropy oxide supports, the problems of low current density and poor stability of noble metal catalysts in alkaline water electrolysis were solved, and a highly efficient and stable water electrolysis hydrogen production process was realized.
Patent Information
- Application Number
- CN202410864727.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-01
- Publication Date
- 2026-02-13
- Estimated Expiration
- 2044-07-01
AI Technical Summary
Existing precious metal catalysts suffer from low current density, high cost, and poor stability in alkaline water electrolysis, which limits the efficiency and industrial application of hydrogen production through water electrolysis.
Ruthenium single-atom catalysts were prepared by using ultrafine high-entropy oxides as supports and through steps such as ball milling, calcination, stirring, washing and γ-ray irradiation. The unique properties of high-entropy oxides and the strong penetrability of γ-rays were utilized to form electrocatalysts with strong stability and high specific surface area.
It improves the stability and activity of the catalyst, enhances the efficiency of hydrogen production through water electrolysis, reduces the amount of precious metals used, and has good prospects for industrial application.
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Figure CN118724188B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the technical field of electrolysis of water, in particular to a superfine high-entropy oxide carrier loaded ruthenium monatomic catalyst and a preparation method and application thereof. BACKGROUND
[0002] With the aggravation of environmental pollution problems caused by the consumption of non-renewable energy, the proportion of emerging energy replacing fossil energy is becoming larger and larger. Among many new energy sources, hydrogen energy is an environmentally friendly energy source with obvious advantages and can be obtained through various methods. Among them, electrolysis of water to produce hydrogen has the advantages of simple process and abundant water resources, but the slow kinetics of the oxygen evolution reaction limits the development of water electrolysis. Generally, catalysts are needed to reduce the overpotential of the reaction and thus improve the efficiency of water electrolysis to produce hydrogen.
[0003] The most widely used way of current industrialized water electrolysis is to carry out electrolysis under alkaline conditions, but there are many problems such as small current density. PEM water electrolysis has high current density, fast response and high purity of hydrogen produced, but the working environment is harsh and the required catalyst is limited to noble metal catalysts such as RuO2 and IrO x , which are expensive and have many factors that seriously limit their industrialization. Therefore, the key is to study the utilization rate and catalytic stability of acid water electrolysis catalysts of noble metal catalysts.
[0004] High-entropy oxides can also be called entropy-stable oxides, multi-component oxides, etc., and have high-entropy effect, lattice distortion effect, delayed diffusion effect and cocktail effect, can form many oxygen defects, have high oxygen mobility, rich active sites, thermal / chemical stability and potential synergistic effect, etc. It is of great significance to develop a high-activity and high-stability water electrolysis catalyst by using high-entropy oxides. SUMMARY
[0005] One of the purposes of the application is to provide a preparation method of a superfine high-entropy oxide carrier loaded ruthenium monatomic catalyst with high activity and high stability.
[0006] The second purpose of the application is to provide a superfine high-entropy oxide carrier loaded ruthenium monatomic catalyst prepared by the above method.
[0007] The third purpose of the application is to provide an application of the above superfine high-entropy oxide carrier loaded ruthenium monatomic catalyst.
[0008] To achieve the above purposes, the technical scheme adopted by the application is:
[0009] A preparation method of a superfine high-entropy oxide carrier loaded ruthenium monatomic catalyst, comprising the following steps:
[0010] 1) Ball-milling manganese source, cobalt source, copper source, nickel source, iron source and fumed silica for 0.5-2h, then drying, ball-milling again for 20-36h to obtain a precursor;
[0011] 2) Calcining the precursor obtained in step 1) at 900-1200℃ for 10-15h, cooling to obtain a high-entropy material;
[0012] 3) Adding the high-entropy material obtained in step 2) into an alkali solution, stirring for 6-10h, then washing, vacuum drying for 10-24h to obtain an ultrafine material;
[0013] 4) Mixing the ultrafine material obtained in step 3) with a ruthenium source in water, adjusting pH to 1-2.5, then passing inert gas to remove oxygen, sealing, then irradiating with γ-ray, then washing, drying to obtain the product.
[0014] The type and ratio of metal elements in the transition metal high-entropy oxide can be adjusted, and the special high-entropy effect can provide a coordination environment and bonding effect for anchoring different types of noble metal single atoms.
[0015] In the single-atom catalyst, the strong metal-support interaction, low coordination environment and quantum size effect between the single atom and the oxide support can better disperse to improve the catalytic activity and reduce the use of noble metals. Anchoring noble metal atoms on the substrate can greatly improve the atomic utilization rate and stability of noble metals, and has unique electronic structure and excellent catalytic performance.
[0016] The manganese source in step 1) is any one of manganese chloride, manganese nitrate and manganese sulfate.
[0017] The cobalt source in step 1) is any one of cobalt chloride, cobalt nitrate and cobalt sulfate.
[0018] The nickel source in step 1) is any one of nickel chloride, nickel nitrate and nickel sulfate.
[0019] The iron source in step 1) is any one of iron chloride, iron nitrate and iron sulfate.
[0020] The molar ratio of manganese source, cobalt source, copper source, nickel source and iron source in step 1) is 1:1-2:1-2:1-2:1-2. Preferably, the molar ratio of manganese source, cobalt source, copper source, nickel source and iron source is 1:1:1:1:1.
[0021] The molar ratio of fumed silica and manganese source in step 1) is 1-2:1, preferably the molar ratio of fumed silica and manganese source is 1:1.
[0022] The calcination in step 2) is in air atmosphere.
[0023] The temperature rising speed in step 2) is 3-8 ℃ / min.
[0024] The alkali solution in step 3) is any one of sodium hydroxide solution and potassium hydroxide solution.
[0025] The washing in step 3) is washing with water.
[0026] The temperature for vacuum drying in step 3) is 35-50 ℃.
[0027] The mass ratio of the ultrafine material to the ruthenium source in step 4) is 2-4:1.
[0028] The ruthenium source in step 4) is any one of ruthenium trichloride, ruthenium acetylacetonate, ruthenium acetate and ruthenium oxide.
[0029] The pH adjustment in step 4) is adjusted by sulfuric acid.
[0030] The inert gas in step 4) is any one of nitrogen and argon.
[0031] The gamma ray in step 4) is 60 The gamma ray of Co.
[0032] Beneficial effects:
[0033] The ultrafine high-entropy oxide supported ruthenium monatomic catalyst disclosed by the application is based on the requirement of acidic electrolytic water, the carrier is a transition metal composed ultrafine high-entropy oxide, the unique properties of the high-entropy oxide are utilized, the high-entropy oxide itself can be used as a catalyst for acidic electrolytic water, and the performance of the catalyst can be greatly improved. The ultrafine high-entropy oxide is obtained by a silica template method, the specific surface area of the high-entropy oxide is greatly improved, and the stability, active site, loading capacity and catalytic performance of the monatomic supported catalyst are improved. Further, the strong penetration of the gamma ray helps to form nanoparticles and defect carriers at the same time, and is bridged through metal-oxygen bonds, so that the structural stability and active site exposure are ensured, and the performance of the catalyst is further enhanced.
[0034] The preparation process of the application mainly uses a template method for mechanical alloying and uses gamma rays for irradiation treatment, realizes the anchoring of ruthenium monatomic in high-entropy oxide, forms an electrocatalyst with strong stability and high specific surface area, has the advantages of strong process stability, simple operation, low cost and large-scale preparation, and has great industrial application prospect. BRIEF DESCRIPTION OF DRAWINGS
[0035] Figure 1The XRD comparison chart of the ultrafine high-entropy oxide (MnFeCoNiCu)2O4 and the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst prepared in embodiment 2 of the present application.
[0036] Figure 2 The OER performance chart of the ultrafine high-entropy oxide (MnFeCoNiCu)2O4 and the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst prepared in embodiment 2 of the present application in 0.5 mol / L H2SO4 solution.
[0037] Figure 3 The stability chart of the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst prepared in embodiment 2 of the present application in 0.5 mol / L H2SO4 solution at 10 mA cm-2. -1
[0038] Figure 4 The OER performance chart of the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalysts with different ruthenium loadings prepared in embodiments 1, 2 and 3 in 0.5 mol / L H2SO4 solution. DETAILED DESCRIPTION
[0039] In order to make the technical problems solved by the present application, the technical solutions adopted and the technical effects achieved more easily understood, the technical solutions of the present application will be clearly and completely described below in conjunction with specific embodiments.
[0040] Embodiment 1
[0041] The preparation method of the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst of the present embodiment comprises the following steps:
[0042] 1) 1 mol of manganese chloride, 1 mol of cobalt chloride hexahydrate, 1 mol of copper chloride, 1 mol of nickel chloride hexahydrate, 1 mol of ferric chloride and 1 mol of fumed silica are added to a ball mill jar, high-speed grinding for half an hour, opening the drying, and then continuing ball milling for 24 h to obtain a precursor;
[0043] 2) The precursor prepared in step 1) is calcined at 900℃ for 12 h in an air environment, and then cooled to room temperature to obtain a sample (MnFeCoNiCu)2O4@SiO2;
[0044] 3) The (MnFeCoNiCu)2O4@SiO2 sample prepared in step 2) is added to a 2.5 M (mol / L) NaOH solution, stirred at room temperature for 8 h, then washed with deionized water, repeated 4 times to remove the silica gel template, and then dried under vacuum at 40℃ overnight to finally obtain an ultrafine sample (MnFeCoNiCu)2O4;
[0045] 4) Weigh 10 mg of anhydrous ruthenium trichloride into 20 mL of deionized water, add 60 mg of (MnFeCoNiCu)2O4 prepared in step 3) to the above solution, adjust the pH to 2 with a 0.5 mol / L H2SO4 solution, then bubble N2 into the solution to remove oxygen in the solution, then seal the solution, and 60 After the end of the irradiation, the solution is washed with ethanol and water, and the ultrafine high-entropy oxide supported ruthenium monatomic catalyst is obtained after drying.
[0046] Example 2
[0047] The preparation method of the ultrafine high-entropy oxide carrier supported ruthenium monatomic catalyst of the present embodiment comprises the following steps:
[0048] 1) Put 1 mol of manganese chloride, 1 mol of cobalt chloride hexahydrate, 1 mol of copper chloride, 1 mol of nickel chloride hexahydrate, 1 mol of ferric chloride, and 1 mol of fumed silica into a ball mill jar, high-speed grind for half an hour, open the drying, and then continue to ball mill for 24 h to obtain a precursor;
[0049] 2) The precursor prepared in step 1) is calcined at 900°C for 12 h in an air environment, and then cooled to room temperature to obtain a sample (MnFeCoNiCu)2O4@SiO2;
[0050] 3) The (MnFeCoNiCu)2O4@SiO2 sample prepared in step 2) is added to a 2.5M NaOH solution, stirred at room temperature for 8 h, then washed with deionized water, and repeated 4 times to remove the silica gel template, and then dried at 40°C under vacuum conditions overnight to obtain an ultrafine sample (MnFeCoNiCu)2O4;
[0051] 4) Weigh 20 mg of anhydrous ruthenium trichloride into 20 mL of deionized water, add 60 mg of (MnFeCoNiCu)2O4 prepared in step 3) to the above solution, adjust the pH to 2 with a 0.5 mol / L H2SO4 solution, then bubble N2 into the solution to remove oxygen in the solution, then seal the solution, and 60 After the end of the irradiation, the solution is washed with ethanol and water, and the ultrafine high-entropy oxide supported ruthenium monatomic catalyst is obtained after drying.
[0052] Example 3
[0053] The preparation method of the ultrafine high-entropy oxide carrier supported ruthenium monatomic catalyst of the present embodiment comprises the following steps:
[0054] 1) 1 mol of manganese chloride, 1 mol of cobalt chloride hexahydrate, 1 mol of copper chloride, 1 mol of nickel chloride hexahydrate, 1 mol of ferric chloride and 1 mol of fumed silica are added to a ball mill jar, high-speed grinding for half an hour, opening drying, and then continuing ball milling for 24 h to obtain a precursor;
[0055] 2) The precursor prepared in step 1) is calcined at 900°C for 12 h in an air environment, and then cooled to room temperature to obtain a sample (MnFeCoNiCu)2O4@SiO2;
[0056] 3) The (MnFeCoNiCu)2O4@SiO2 sample prepared in step 2) is added to a 2.5M NaOH solution, stirred at room temperature for 8 h, then washed with deionized water, repeated 4 times to remove the silica gel template, and then dried under vacuum at 40°C overnight to obtain a superfine sample (MnFeCoNiCu)2O4;
[0057] 4) 30 mg of anhydrous ruthenium trichloride is weighed into 20 mL of deionized water, 60 mg of (MnFeCoNiCu)2O4 prepared in step 3) is added to the above solution, 0.5 mol / L H2SO4 solution is used to adjust the PH to 2, then N2 is introduced into the solution to remove oxygen in the solution, and then the solution is sealed, irradiated with a γ-ray radiation source of Co, and after the end of the irradiation, washed with ethanol and water, and dried to obtain a superfine high-entropy oxide supported ruthenium monatomic catalyst. 60 Co is used for irradiation, and after the end of the irradiation, washed with ethanol and water, and dried to obtain a superfine high-entropy oxide supported ruthenium monatomic catalyst.
[0058] Example 4
[0059] The preparation method of the superfine high-entropy oxide carrier supported ruthenium monatomic catalyst of the present embodiment is different from that of Example 1 in that the precursor in step 2) is calcined at 1000°C for 12 h in an air environment, and the others are the same as in Example 1.
[0060] Example 5
[0061] The preparation method of the superfine high-entropy oxide carrier supported ruthenium monatomic catalyst of the present embodiment is different from that of Example 2 in that the precursor in step 2) is calcined at 1100°C for 12 h in an air environment, and the others are the same as in Example 2.
[0062] Example 6
[0063] The preparation method of the superfine high-entropy oxide carrier supported ruthenium monatomic catalyst of the present embodiment is different from that of Example 3 in that the precursor in step 2) is calcined at 1200°C for 12 h in an air environment, and the others are the same as in Example 3.
[0064] Example 7
[0065] The difference between the preparation method of the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst of the embodiment and that of embodiment 1 is that the amount of cobalt chloride hexahydrate in step 1) is 2 mol, and the others are the same as in embodiment 1.
[0066] Embodiment 8
[0067] The difference between the preparation method of the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst of the embodiment and that of embodiment 7 is that the amount of anhydrous ruthenium chloride in step 4) is 20 mg, and the others are the same as in embodiment 7.
[0068] Embodiment 9
[0069] The difference between the preparation method of the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst of the embodiment and that of embodiment 7 is that the amount of anhydrous ruthenium chloride in step 4) is 30 mg, and the others are the same as in embodiment 7.
[0070] Experimental example
[0071] (1) XRD test
[0072] The ultrafine high-entropy oxide (MnFeCoNiCu) 2O4 and the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst prepared in embodiment 2 were taken for XRD test, and the test results are shown in Figure 1
[0073] From Figure 1 It can be seen that the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst prepared by the application has a single crystal structure.
[0074] (2) OER performance test
[0075] The ultrafine high-entropy oxide (MnFeCoNiCu) 2O4 and the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst prepared in embodiment 2 were taken to test their OER performance in 0.5 mol / L H 2 SO 4 solution, and the results are shown in Figure 2 、 Figure 3 、 Figure 4
[0076] The above experimental results show that the ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst prepared by the application has good performance in industrialized PEM electrolytic water.
[0077] The ultrafine high-entropy oxide carrier loaded ruthenium monatomic catalyst prepared by the application has high stability and catalytic activity, does not need to be prepared in a special environment, and can be prepared on a large scale. Especially under the condition of the optimal amount of anhydrous ruthenium chloride and equimolar transition metal salt, the best electrochemical performance is obtained.
[0078] The above merely illustrates the preferred embodiments and experimental examples of the present application, and is not intended to limit the protection scope of the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. A method for preparing an ultrafine high-entropy oxide support loaded ruthenium monatomic catalyst, characterized in that, It comprises the following steps: 1) Ball-milling a manganese source, a cobalt source, a copper source, a nickel source, an iron source and fumed silica for 0.5-2 h, then drying, and ball-milling again for 20-36 h to obtain a precursor; 2) Calcining the precursor obtained in step 1) at 900-1200 ℃ for 10-15 h, cooling to obtain a high-entropy material; 3) Adding the high-entropy material obtained in step 2) into an alkali solution, stirring for 6-10 h, then washing, and vacuum drying for 10-24 h to obtain an ultrafine material; 4) Mixing the ultrafine material obtained in step 3) with a ruthenium source in water, adjusting the pH to 1-2.5, then passing in an inert gas to remove oxygen, sealing, and irradiating with γ rays, then washing and drying.
2. The method for preparing ruthenium single-atom catalyst supported on an ultrafine high-entropy oxide support according to claim 1, characterized in that, The manganese source in step 1) is any one of manganese chloride, manganese nitrate and manganese sulfate; the cobalt source is any one of cobalt chloride, cobalt nitrate and cobalt sulfate; the nickel source is any one of nickel chloride, nickel nitrate and nickel sulfate; and the iron source is any one of iron chloride, iron nitrate and iron sulfate.
3. The method for preparing ruthenium single-atom catalyst supported on an ultrafine high-entropy oxide support according to claim 2, characterized in that, The molar ratio of manganese in the manganese source, cobalt in the cobalt source, copper in the copper source, nickel in the nickel source and iron in the iron source in step 1) is 1:1-2:1-2:1-2:1-2.
4. The method for preparing ruthenium single-atom catalyst supported on an ultrafine high-entropy oxide support according to claim 3, characterized in that, The molar ratio of manganese in the manganese source, cobalt in the cobalt source, copper in the copper source, nickel in the nickel source and iron in the iron source in step 1) is 1:1:1:1:
1.
5. The method for preparing ruthenium single-atom catalyst supported on an ultrafine high-entropy oxide support according to claim 1, characterized in that, The mass ratio of the ultrafine material to the ruthenium source in step 4) is 2-4:
1.
6. The method for preparing ruthenium single-atom catalyst supported on an ultrafine high-entropy oxide support according to claim 1, characterized in that, The ruthenium source in step 4) is any one of ruthenium trichloride, ruthenium acetylacetonate, ruthenium acetate and ruthenium oxide.
7. The method for preparing ruthenium single-atom catalyst supported on an ultrafine high-entropy oxide support according to claim 1, characterized in that, The irradiation time in step 4) is 4-8 h.
8. The method for preparing ruthenium single-atom catalyst supported on an ultrafine high-entropy oxide support according to claim 1, characterized in that, The absorbed dose is 60-80 kGy, and the dose rate is 8.5 kGy / h.
9. An ultrafine high-entropy oxide carrier supported ruthenium monatomic catalyst prepared by the method of claim 1.
10. Use of the ultrafine high-entropy oxide carrier supported ruthenium monatomic catalyst of claim 9 in industrialized PEM electrolytic water.
Citation Information
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