Perovskite catalyst and preparation method and application thereof
Synthesis of copper-based perovskite-type oxide catalysts doped with metal ions by sol-gel method solves the problem of difficulty in preparing copper-based perovskite-type oxide catalysts in the prior art, and realizes efficient and low-cost catalyst preparation, which is suitable for the field of electrolytic water catalysts.
Patent Information
- Application Number
- CN202411670627.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-21
- Publication Date
- 2025-03-04
AI Technical Summary
In the prior art, it is difficult to efficiently prepare copper-based perovskite oxide catalysts, and precious metal catalysts are expensive, which limits their wide application.
The sol-gel method was used to synthesize copper-based perovskite oxide catalysts doped in metal ions in different countries. A highly efficient perovskite catalyst was prepared by placing the M in LaCuXM(1-X)O3 as Fe, Co, Ni or Zn, 0.1≤X≤0.5.
It has achieved efficient, simple, stable and low-cost perovskite catalyst preparation, with high crystallinity and good stability, suitable for industrial production, and has shown good application prospects in the field of electrolytic catalysts.
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Figure CN119549139A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of water electrolysis catalysts, and in particular to a perovskite catalyst and a preparation method and application thereof. Background Art
[0002] Due to energy shortage, it is urgent to find new renewable energy sources. However, after more than a decade of research, it has been found that hydrogen energy is one of the best choices. Among the many methods of hydrogen production, the method of producing hydrogen by electrolysis of water has always attracted much attention. For the overall process of water electrolysis reaction, the main rate-limiting step is still the oxygen evolution reaction. Therefore, finding a suitable catalyst has become one of the research hotspots, and the research on catalyst materials is also diverse. Among them, precious metal catalysts have the best performance so far, but their high price limits their large-scale application.
[0003] The general formula of perovskite oxides is ABO3, where the A-site atom is a rare earth metal, alkaline earth metal or alkali metal with a larger radius. This ion itself is not active and only plays a role in stabilizing the structure of the perovskite and regulating the B-site ion. The B-site ion, which is generally a metal ion with a 3d, 4d, or 5d electronic configuration, has catalytic activity. During the preparation process, it is possible to partially replace the B element to change its structure, thereby changing its performance in water electrolysis catalysis. Therefore, transition metal ion doping has the prospect of in-depth research in the field of perovskites. Summary of the invention
[0004] The purpose of the present invention is to provide a perovskite catalyst, a preparation method and an application thereof, and to provide an efficient, simple, stable and low-cost preparation method to solve the technical problems existing in the prior art in order to solve the problem of difficulty in efficiently preparing copper-based perovskite-type oxides.
[0005] In order to solve the above technical problems, the present invention specifically provides the following technical solutions:
[0006] A method for preparing a perovskite catalyst comprises the following steps:
[0007] 1) La(NO3)3·6H2O, Cu(NO3)2·3H2O, Fe(NO3)3·9H2O, Co(NO3)2·6H2O, Ni(NO3)2·6H2O and Zn(NO3)2·6H2O were added into deionized water and dissolved to obtain a mixture solution A;
[0008] 2) C6H8O7·H2O and C2H6O2 are added to deionized water and mixed to obtain a mixture solution B;
[0009] 3) slowly adding the mixture solution B into the mixture solution A and mixing them evenly to obtain a mixture solution C;
[0010] 4) maintaining the mixture solution C at a certain temperature and stirring continuously until the mixture becomes a gel;
[0011] 5) placing the gel-like mixture in an oven and drying it to obtain a mixture D;
[0012] 6) Grinding the mixture D into powder;
[0013] 7) The ground powder is placed in a muffle furnace and calcined at a certain temperature to obtain the target product.
[0014] Furthermore, in step 3), the molar ratio of metal ions to citric acid in the mixture solution C is 1:1.5.
[0015] Furthermore, in step 4), the temperature is maintained at 80°C.
[0016] Furthermore, in step 5), the temperature of the oven is set to 150° C. and the drying is performed for 10 hours.
[0017] Furthermore, in the step 7), the calcination temperature in the muffle furnace is 600° C., the heating rate is 5° C. / min, and the temperature is kept at this temperature for 180 minutes.
[0018] In order to solve the above technical problems, the present invention further provides the following technical solutions:
[0019] A perovskite catalyst has the formula LaCu X M (1-X) O3;
[0020] Wherein, M is Fe, Co, Ni or Zn, and 0.1≤X≤0.5.
[0021] In order to solve the above technical problems, the present invention further provides the following technical solutions:
[0022] An application of a perovskite catalyst, characterized in that it is used as a catalyst for oxygen evolution reaction in water electrolysis reaction.
[0023] Compared with the prior art, the present invention has the following beneficial effects:
[0024] The sol-gel method adopted in the present invention prepares copper-based perovskite-type oxide catalytic materials doped with metal ions from different countries, which have high crystallinity, good material stability, simple preparation process and low price, can be industrially produced, and also have good application prospects in the field of water electrolysis catalysts. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] In order to more clearly illustrate the implementation methods of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for the implementation methods or the description of the prior art. Obviously, the drawings in the following description are only exemplary, and for ordinary technicians in this field, other implementation drawings can be derived from the provided drawings without creative work.
[0026] Figure 1 The SEM images of the prepared copper-based perovskite oxides doped with different transition metal ions;
[0027] Figure 2 LSV diagram of the prepared copper-based perovskite oxides doped with different transition metal ions. DETAILED DESCRIPTION
[0028] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0029] like Figure 1 As shown, the present invention provides a method for preparing a perovskite catalyst, wherein a Fe compound, a Co compound, a Ni compound or a Zn compound is used as a reactant, citric acid and an ethylene glycol solution are used as a complexing agent for the reaction, and a transition metal-doped copper-based perovskite-type oxide catalyst material is obtained by synthesizing it by a sol-gel method and then calcining it.
[0030] The specific steps are as follows.
[0031] 1) Lanthanum nitrate hexahydrate (La(NO3)3·6H2O), copper nitrate trihydrate (Cu(NO3)2·3H2O), iron nitrate nonahydrate (Fe(NO3)3·9H2O) / cobalt nitrate hexahydrate (Co(NO3)2·6H2O) / nickel nitrate hexahydrate (Ni(NO3)2·6H2O) / zinc nitrate hexahydrate (Zn(NO3)2·6H2O) are added to deionized water and dissolved to obtain a mixture solution A.
[0032] 2) Add citric acid (C6H8O7·H2O) and ethylene glycol (C2H6O2) to deionized water and mix them to obtain a mixture solution B.
[0033] 3) Slowly adding the mixture solution B into the mixture solution A and mixing them evenly to obtain a mixture solution C; wherein the molar ratio of the metal ions to the citric acid in the mixture solution C is 1:1.5.
[0034] 4) Maintain the mixture solution C at a certain temperature and stir continuously until the mixture becomes a gel; the temperature is maintained at 80°C.
[0035] 5) The gel-like mixture was placed in an oven and dried to obtain a mixture D; the temperature of the oven was set at 150° C. and dried for 10 hours.
[0036] 6) Grind the mixture D into powder.
[0037] 7) The ground powder is placed in a muffle furnace and calcined at a certain temperature to obtain the target product; the calcination temperature in the muffle furnace is 600°C, the heating rate is 5°C / min, and the temperature is kept for 180 minutes.
[0038] Embodiment 1:
[0039] 1) Lanthanum nitrate hexahydrate (La(NO3)3·6H2O) and copper nitrate trihydrate (Cu(NO3)2·3H2O) were added to deionized water and dissolved to obtain a mixture solution A.
[0040] 2) Add citric acid (C6H8O7·H2O) and ethylene glycol (C2H6O2) to deionized water and mix them to obtain a mixture solution B.
[0041] 3) Slowly adding the mixture solution B into the mixture solution A and mixing them evenly to obtain a mixture solution C, wherein the molar ratio of the metal ions to the citric acid is 1:1.5.
[0042] 4) Maintain the mixture solution C at 80° C. and stir continuously until the mixture becomes a gel.
[0043] 5) The gel-like mixture was placed in an oven and dried at 150° C. for 10 h to obtain a mixture D.
[0044] 6) Grind the mixture D into powder.
[0045] 7) The ground powder was placed in a muffle furnace at 600°C, kept warm for 3 hours, with a heating rate of 5°C / min, and calcined to obtain the target product.
[0046] Embodiment 2:
[0047] 1) Lanthanum nitrate hexahydrate (La(NO3)3·6H2O), copper nitrate trihydrate (Cu(NO3)2·3H2O) and iron nitrate nonahydrate (Fe(NO3)3·9H2O) were dissolved in deionized water to obtain a mixture solution A.
[0048] 2) Add citric acid (C6H8O7·H2O) and ethylene glycol (C2H6O2) to deionized water and mix them to obtain a mixture solution B.
[0049] 3) Slowly adding the mixture solution B into the mixture solution A and mixing them evenly to obtain a mixture solution C, wherein the molar ratio of the metal ions to the citric acid is 1:1.5.
[0050] 4) Maintain the mixture solution C at 80° C. and stir continuously until the mixture becomes a gel.
[0051] 5) The gel-like mixture was placed in an oven and dried at 150° C. for 10 h to obtain a mixture D.
[0052] 6) Grind the mixture D into powder.
[0053] 7) The ground powder was placed in a muffle furnace at 600°C, kept warm for 3 hours, with a heating rate of 5°C / min, and calcined to obtain the target product.
[0054] Embodiment 3:
[0055] 1) Lanthanum nitrate hexahydrate (La(NO3)3·6H2O), copper nitrate trihydrate (Cu(NO3)2·3H2O) and cobalt nitrate hexahydrate (Co(NO3)2·6H2O) were dissolved in deionized water to obtain a mixture solution A.
[0056] 2) Add citric acid (C6H8O7·H2O) and ethylene glycol (C2H6O2) to deionized water and mix them to obtain a mixture solution B.
[0057] 3) Slowly adding the mixture solution B into the mixture solution A and mixing them evenly to obtain a mixture solution C, wherein the molar ratio of the metal ions to the citric acid is 1:1.5.
[0058] 4) Maintain the mixture solution C at 80° C. and stir continuously until the mixture becomes a gel.
[0059] 5) The gel-like mixture was placed in an oven and dried at 150° C. for 10 h to obtain a mixture D.
[0060] 6) Grind the mixture D into powder.
[0061] 7) The ground powder was placed in a muffle furnace at 600°C for 3 h at a heating rate of 5°C / min to calcine the target product.
[0062] Embodiment 4:
[0063] 1) Lanthanum nitrate hexahydrate (La(NO3)3·6H2O), copper nitrate trihydrate (Cu(NO3)2·3H2O) and nickel nitrate hexahydrate (Ni(NO3)2·6H2O) were dissolved in deionized water to obtain a mixture solution A.
[0064] 2) Add citric acid (C6H8O7·H2O) and ethylene glycol (C2H6O2) to deionized water and mix them to obtain a mixture solution B.
[0065] 3) Slowly adding the mixture solution B into the mixture solution A and mixing them evenly to obtain a mixture solution C, wherein the molar ratio of the metal ions to the citric acid is 1:1.5.
[0066] 4) Maintain the mixture solution C at 80° C. and stir continuously until the mixture becomes a gel.
[0067] 5) The gel-like mixture was placed in an oven and dried at 150° C. for 10 h to obtain a mixture D.
[0068] 6) Grind the mixture D into powder.
[0069] 7) The ground powder was placed in a muffle furnace at 600°C for 3 h at a heating rate of 5°C / min to calcine the target product.
[0070] Embodiment 5:
[0071] 1) Lanthanum nitrate hexahydrate (La(NO3)3·6H2O), copper nitrate trihydrate (Cu(NO3)2·3H2O) and zinc nitrate hexahydrate (Zn(NO3)2·6H2O) were dissolved in deionized water to obtain a mixture solution A.
[0072] 2) Add citric acid (C6H8O7·H2O) and ethylene glycol (C2H6O2) to deionized water and mix them to obtain a mixture solution B.
[0073] 3) Slowly adding the mixture solution B into the mixture solution A and mixing them evenly to obtain a mixture solution C, wherein the molar ratio of the metal ions to the citric acid is 1:1.5.
[0074] 4) Maintain the mixture solution C at 80° C. and stir continuously until the mixture becomes a gel.
[0075] 5) The gel-like mixture was placed in an oven and dried at 150° C. for 10 h to obtain a mixture D.
[0076] 6) Grind the mixture D into powder.
[0077] 7) The ground powder was placed in a muffle furnace at 600°C for 3 h at a heating rate of 5°C / min to calcine the target product.
[0078] The present invention also discloses the chemical formula of the perovskite catalyst, which is LaCu X M (1-X) O3, (M=Fe, Co, Ni, Zn; 0.1≤X≤0.5).
[0079] The invention also discloses an application of a perovskite catalyst as a catalyst for oxygen evolution reaction in water electrolysis reaction.
[0080] The above embodiments are only exemplary embodiments of the present application and are not intended to limit the present application. The protection scope of the present application is defined by the claims. Those skilled in the art may make various modifications or equivalent substitutions to the present application within the essence and protection scope of the present application, and such modifications or equivalent substitutions shall also be deemed to fall within the protection scope of the present application.
Claims
1. A method for preparing a perovskite catalyst, characterized in that: The following steps are involved: 1) La(NO3)3·6H2O, Cu(NO3)2·3H2O, Fe(NO3)3·9H2O, Co(NO3)2·6H2O, Ni(NO3)2·6H2O and Zn(NO3)2·6H2O were added into deionized water and dissolved to obtain a mixture solution A; 2) C6H8O7·H2O and C2H6O2 are added to deionized water and mixed to obtain a mixture solution B; 3) slowly adding the mixture solution B into the mixture solution A and mixing them evenly to obtain a mixture solution C; 4) maintaining the mixture solution C at a certain temperature and stirring continuously until the mixture becomes a gel; 5) placing the gel-like mixture in an oven and drying it to obtain a mixture D; 6) Grinding the mixture D into powder; 7) The ground powder is placed in a muffle furnace and calcined at a certain temperature to obtain the target product.
2. The method according to claim 1, characterized in that: In the step 3), the molar ratio of metal ions to citric acid in the mixture solution C is 1:1.
5.
3. The method according to claim 1, characterized in that: In step 4), the temperature is maintained at 80°C.
4. The method according to claim 1, characterized in that: In the step 5), the temperature of the oven is set to 150° C. and the drying is performed for 10 hours.
5. The method according to claim 1, characterized in that: In the step 7), the calcination temperature in the muffle furnace is 600° C., the heating rate is 5° C. / min, and the temperature is kept for 180 minutes.
6. A perovskite catalyst prepared according to the method of any one of claims 1 to 5 has a chemical formula of LaCu X M (1-X) O3; in, M is Fe, Co, Ni or Zn, 0.1≤X≤0.
5.
7. Use of the perovskite catalyst prepared by the method according to any one of claims 1 to 5, characterized in that: As a catalyst for oxygen evolution reaction in water electrolysis.