CN113697767A - Preparation method of magnesium-based hydrogen storage composite material - Google Patents

Preparation method of magnesium-based hydrogen storage composite material Download PDF

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CN113697767A
CN113697767A CN202111015311.1A CN202111015311A CN113697767A CN 113697767 A CN113697767 A CN 113697767A CN 202111015311 A CN202111015311 A CN 202111015311A CN 113697767 A CN113697767 A CN 113697767A
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程颖
石碧清
董冰
纪献兵
李思琪
梁赟
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Hebei University of Environmental Engineering
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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Abstract

The invention discloses a preparation method of a magnesium-based hydrogen storage composite material, which sequentially passes through MgH2The preparation of the material, the preparation of the additive and the ball milling of the composite material, wherein the method prepares the solid solution Ce0.8Co0.1Zr0.1O2Or Ce0.8Mn0.1Zr0.1O2Sample, and adding it to MgH2In the method, the magnesium-based hydrogen storage composite material is prepared by ball milling, the preparation method is simple, the process is easy to control, and the material is compared with MgH2The hydrogen absorption/desorption rate and the hydrogen storage capacity are greatly improved, and the dynamic performance is better. The method is suitable for preparing the magnesium-based hydrogen storage composite material.

Description

Preparation method of magnesium-based hydrogen storage composite material
Technical Field
The invention belongs to the field of hydrogen storage material preparation, and particularly relates to a preparation method of a magnesium-based hydrogen storage alloy composite material.
Background
The combustion of fossil fuel and the emission of greenhouse gases cause great pollution to the environment, and the search for clean and pollution-free new energy to replace traditional energy materials is urgent. Hydrogen energy is valued by governments of various countries due to the advantages of abundant resources, high energy density, environmental protection, no pollution and the like, and the effective development and utilization of hydrogen energy need to solve three key problems of hydrogen preparation, storage and transportation and application. Due to the characteristic that hydrogen is extremely easy to catch fire and explode, the problem of solving the storage and transportation of hydrogen becomes a core problem for developing and utilizing hydrogen energy. The traditional high-pressure gaseous hydrogen storage and liquid hydrogen storage have poor safety and high cost, and solid hydrogen storage technology which is popular in recent years is concerned with due to the advantages of high safety, high hydrogen storage density, convenient transportation and the like.
Among the numerous solid-state hydrogen storage materials, magnesium-based hydrides (MgH)2) The vehicle-mounted hydrogen storage material has high hydrogen storage capacity (7.6 wt.%), low price and abundant resources, and the hydrogen storage density of the vehicle-mounted hydrogen storage material meets the requirements of the international energy agency on the vehicle-mounted hydrogen energy system (the hydrogen storage capacity is more than or equal to 6.5 wt.%), so the vehicle-mounted hydrogen storage material has great development potential. However, the practical application of the method is limited by the disadvantages of slow hydrogen absorption and desorption rate, high hydrogen desorption temperature (400 ℃), easy formation of a dense oxide film on the surface and the like. Therefore, the key to reducing the stability of magnesium-based hydrides and improving the hydrogen absorption/desorption kinetics is the design and preparation of highly active, highly stable catalysts.
Disclosure of Invention
The invention aims to provide a preparation method of a magnesium-based hydrogen storage alloy composite material, which prepares a solid solution Ce0.8Co0.1Zr0.1O2Or Ce0.8Mn0.1Zr0.1O2Sample, and adding it to MgH2In the method, the magnesium-based hydrogen storage composite material is prepared by ball milling, and compared with MgH2The hydrogen absorption and desorption rate and the hydrogen storage capacity are greatly improved, and the dynamic performance is better.
The technical scheme of the invention is as follows:
the preparation method of the magnesium-based hydrogen storage composite material comprises the following steps:
(1)MgH2preparation of the Material
Putting a certain amount of Mg powder into a hydrogenation tube, and fully reacting at 400 ℃ and 4Mpa hydrogen pressure to prepare MgH2A material;
(2) preparation of the additives
(21) Dissolving cerium salt in a mixed solvent of methanol and water, and after ultrasonic treatment and uniform mixing, marking the solution as A;
(22) dissolving zirconium oxychloride in a mixed solvent of ethylene glycol and water, and after ultrasonic treatment and uniform mixing, marking the solution as B;
(23) dissolving cobalt salt or manganese salt in deionized water, and marking the solution as C after ultrasonic treatment and uniform mixing;
(24) dropwise adding the solution B into the solution A at a dropwise adding rate of 0.1mL/s, uniformly mixing, continuously stirring for 2 hours to obtain a mixed solution, dropwise adding the solution C into the mixed solution, and stirring for 1 hour in a sealed manner to obtain a solution D;
in the step, the dropping rate of the B solution is crucial, which influences the formation of Ce-Zr base, and when the dropping rate of B is too high, the combination of cerium salt and zirconium salt is insufficient; when the dropping speed of B is too slow, Ce-Zr base is not easy to form;
(25) adding a surfactant into the solution D, continuously stirring for 30min after the surfactant is completely dissolved, then dropwise adding a precipitator into the solution, adjusting the pH value to be alkaline, continuously stirring for 2h, and aging for 24h under a vacuum condition at room temperature after the stirring is finished to obtain E;
in the present invention, the surfactant plays a key role in crosslinking during the preparation process, and the added content thereof affects the formation and structure of the final solid solution, and the molar volume ratio (unit is mol/L) of the surfactant to D in this step is 1: 15, the concentration of the surfactant is 2 mol/L; when the addition amount is too large, a large amount of surfactant is remained on the surface of the solid solution, so that the purity of the solid solution is influenced, and when the addition amount is too small, metal elements are not easy to enter cerium-based lattices, so that the formation of the solid solution is not facilitated;
(26) centrifuging the E, repeatedly washing the centrifuged product with deionized water and absolute ethyl alcohol for many times, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain F;
(27) placing the F in a muffle furnace for two-stage calcination, wherein the first stage calcination is performed by heating to 250 ℃ at room temperature and keeping the temperature for 2 hours, the second stage calcination is performed by heating to 600 ℃ from 250 ℃ and keeping the temperature for 5 hours, and cooling along with the furnace to room temperature to obtain the additive solid solution Ce0.8Co0.1Zr0.1O2(CCZ) or Ce0.8Mn0.1Zr0.1O2(CMZ) a sample;
the preparation method comprises the steps of preparing the additive solid solution by two-stage calcination, heating the mixture to 250 ℃ from room temperature in the first-stage calcination, gradually removing gas and corresponding water adsorbed on the surface of the F product in the process, and completely removing surface impurities after heat preservation, wherein the purity of the product is influenced; the temperature is increased from 250 ℃ to 600 ℃ in the second stage of calcination, the structure of the cerium-based oxide is preliminarily formed in the process, and metal elements can enter the cerium-based oxide more favorably in the heat preservation process, so that a solid solution containing multi-element metal is finally formed;
(3) ball milling preparation of composite material
MgH is added2And the additive is placed in a ball milling tank under the argon atmosphere, ball milling is carried out under the ball-material ratio of 20:1, the ball milling rotating speed is 350r/min, the ball milling is suspended for 15min every 30min, and the circulation is carried out for 10 times; and (4) taking out the ball milling tank after the ball milling is finished, and naturally cooling at room temperature to obtain the composite material.
As a limitation of the present invention:
in the first step and the step (21), the cerium salt is cerium nitrate hexahydrate or ammonium cerium nitrate.
In the step (23), the cobalt salt is cobalt nitrate hexahydrate, and the manganese salt is manganese sulfate.
(III) in the step (25), the pH is 9-11; the more basic environment favors the formation of oxides, but at pH greater than 11 it does not favor the removal of the surface basic solution, which will further affect the purity of its catalyst.
In the step (25), the surfactant is one of cetyl trimethyl ammonium bromide, ascorbic acid or citric acid, and the surfactant can play a key role in crosslinking, so that metal ions can enter a cerium-based material lattice;
and (V) in the step (25), the precipitator is ammonia water or sodium hydroxide solution.
In the step (27), the heating rate of the first stage of calcination is 2 ℃/min, and the heating rate of the second stage of calcination is 1 ℃/min;
in the calcining process, the heating rate influences the purity and the formation of the product, and further influences the structure of the final product, the heating rate of the first section is slightly higher than that of the second section, and the impurities which are easy to volatilize on the surface of the product are required to be removed by the rapid heating of the first section, so that the purity of the product is ensured; the second section has a slower heating rate, and is more beneficial to activating metal atoms under a high temperature condition, so that metal ions are ensured to enter the cerium-based oxide more easily and be completely combined with the cerium-based oxide to form a complete lattice structure, and finally the formation of solid solution is ensured.
Due to the adoption of the technical scheme, the technical effects are as follows:
1. the solid solution material pair MgH obtained by the method of the invention2The thermodynamic performance of hydrogen absorption/desorption is obviously improved, and pure MgH2Compared with the initial hydrogen discharging temperature, the hydrogen discharging temperature is reduced by 50K.
2. The solid solution material prepared by the method has the advantages of simple preparation method, easy process control and low cost.
3. The solid solution material can obviously improve MgH2The hydrogen absorption/desorption performance is mainly because the valence state of cerium and the distribution condition of hydrogen absorption are changed under the synergistic action of a plurality of metal elements in the catalyst, so that the hydrogen absorption/desorption energy barrier is reduced, the catalyst can be further used in the field of hydrogen storage, has better effect and can be conveniently popularized and applied.
The following description will be provided to further explain the embodiments of the present invention in detail with reference to the accompanying drawings.
Drawings
FIG. 1 is Ce in example 10.8Co0.1Zr0.1O2XRD pattern of the sample;
FIG. 2 is Ce in example 10.8Mn0.1Zr0.1O2XRD pattern of the sample;
FIG. 3 is MgH2And MgH2-Ce0.8Mn0.1Zr0.1O2TPD graph of (a);
FIG. 4 is MgH at 623K2And MgH2-Ce0.8Mn0.1Zr0.1O2A hydrogen discharge comparison chart;
FIG. 5 MgH at 423K2And MgH2-Ce0.8Mn0.1Zr0.1O2Hydrogen absorption contrast;
FIG. 6 shows MgH at 473K2And MgH2-Ce0.8Co0.1Zr0.1O2Hydrogen absorption contrast;
FIG. 7 is Ce prepared from group A in example 60.8Co0.1Zr0.1O2SEM image of the sample.
Detailed Description
In the following examples, commercially available reagents were used as the reagents unless otherwise specified, and conventional experimental methods and detection methods were used as the following experimental methods and detection methods unless otherwise specified.
Example 1 an MgH2-Ce0.8Co0.1Zr0.1O2Method for preparing composite material
This example is a MgH2-Ce0.8Co0.1Zr0.1O2The preparation method of the composite material comprises the following steps:
(1)MgH2preparation of the Material
Putting a certain amount of Mg powder into a hydrogenation tube, reacting at 400 ℃ and 4Mpa hydrogen pressure to prepare MgH2A material;
(2) preparation of the additives
(21) Dissolving cerium nitrate hexahydrate in a mixed solvent of methanol and water (the volume ratio of the methanol to the water is 7:3), and after uniformly mixing by ultrasonic waves, marking the solution as A;
(22) dissolving zirconium oxychloride in a mixed solvent of ethylene glycol and water (the volume ratio of the ethylene glycol to the water is 4:1), and after uniformly mixing by ultrasonic waves, marking the solution as B;
(23) dissolving cobalt nitrate hexahydrate in deionized water, and after uniformly mixing by ultrasonic waves, marking the solution as C;
(24) dropwise adding the solution B into the solution A at the dropwise adding rate of 0.1mL/s, uniformly mixing, continuously stirring for 2 hours to obtain a mixed solution, dropwise adding the solution C into the mixed solution, and stirring in a sealed manner for 1 hour, wherein the molar ratio of cerium salt, cobalt salt or manganese salt to zirconium oxychloride is 8:1:1, obtaining D;
(25) adding a surfactant cetyl trimethyl ammonium bromide (the molar volume ratio of the surfactant to the D is 1: 15, the concentration of the surfactant is 2mol/L), continuously stirring for 30min after complete dissolution, then dropwise adding ammonia water into the solution, adjusting the pH value to 9, continuously stirring for 2h, and aging for 24h under a vacuum condition at room temperature after the stirring is finished to obtain E;
(26) centrifuging the E, repeatedly washing the centrifuged product with deionized water and absolute ethyl alcohol for many times, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain F;
(27) placing the F in a muffle furnace for two-stage calcination, heating the F from room temperature to 250 ℃ at the heating rate of 2 ℃/min in the first stage of calcination, and keeping the temperature for 2 hours, heating the F from 250 ℃ to 600 ℃ at the heating rate of 1 ℃/min in the second stage of calcination, and keeping the temperature for 5 hours, and cooling the F to the room temperature along with the furnace to obtain the additive solid solution Ce0.8Co0.1Zr0.1O2And (3) sampling.
(3) Ball milling preparation of composite material
MgH is added2And the additive is placed in a ball milling tank under the argon atmosphere, ball milling is carried out under the ball-material ratio of 20:1, the ball milling rotating speed is 350r/min, the ball milling is suspended for 15min every 30min, and the circulation is carried out for 10 times; taking out the ball milling tank after the ball milling is finished, and naturally cooling at room temperature to obtain MgH2-Ce0.8Co0.1Zr0.1O2A composite material.
EXAMPLE 2-4 preparation of a magnesium-based Hydrogen storage composite
This example separately prepares a magnesium-based hydrogen storage composite material, and the preparation method is similar to that of example 1, except that: the corresponding technical parameters in the preparation process are different, and the specific technical parameters are shown in the following table:
Figure BDA0003240126220000061
EXAMPLE 5 Performance testing of magnesium-based Hydrogen storage composites
This example performs performance testing on the composite materials prepared in examples 1-4, wherein FIG. 1 and FIG. 2 are respectively a sample Ce prepared by the present invention0.8Co0.1Zr0.1O2XRD pattern of (1) and Ce0.8Mn0.1Zr0.1O2XRD pattern of sample from which the synthesized sample Ce can be known0.8Co0.1Zr0.1O2And Ce0.8Mn0.1Zr0.1O2The XRD profile of the sample was significantly shifted from that of the standard card (PDF #34-0394), indicating that Mn/Co and Zr were incorporated into CeO2Inside, a solid solution is formed.
As can be seen from FIGS. 3 to 6, the solid solution material obtained by the method of the invention can be used as a catalyst to obviously improve MgH2The hydrogen absorption and desorption rate and the thermodynamic property of the catalyst. MgH2-Ce0.8Mn0.1Zr0.1O2The initial dehydrogenation temperature of the composite material is relatively pure MgH2Compared with 50K. Meanwhile, the hydrogen absorption/desorption rate and the hydrogen absorption/desorption amount of the composite material and the pure MgH at different temperatures2Compared with the prior art, the method has great improvement. 623K, MgH2 -Ce0.8Mn0.1Zr0.1O2The hydrogen release of the composite material at 3000s reaches 4.88 wt.%, and the pure MgH2The hydrogen evolution of (a) was significantly lower, only 4.53 wt.%. At 473K, pure MgH2The hydrogen uptake of (1.89) is only 1.89 wt.%, whereas the composite material MgH2-Ce0.8Co0.1Zr0.1O2The hydrogen absorption amount of the catalyst is higher than that of pure MgH2Approximately one-fold, specifically 3.50 wt.%. Thus, the addition of the composite material is to MgH2The dynamic and thermodynamic properties of the catalyst play a role in promoting catalysis.
Example 6 comparative example
Group A: this group of additives prepared for the composite material prepared in example 1 was of a disordered structure.
Group B: similar to example 1, except that the preparation method of the additive was different, the specific preparation method was as follows:
under the stirring speed of 200r/min, 0.176g of ammonium ceric nitrate, 0.061g of manganese sulfate and 0.129 g of zirconium oxychloride (wherein the molar ratio of the ammonium ceric nitrate to the manganese sulfate to the zirconium oxychloride is 8:1:1) are dissolved in a mixed solution of absolute ethyl alcohol and methanol, and then the solution is uniformly stirred at 25 ℃ to form a precursor solution; weighing 6g of template agent polymethyl methacrylate (PMMA), adding the template agent PMMA into a precursor solution, dipping for 12 hours at normal temperature (15-25 ℃), then carrying out suction filtration, and drying the obtained solid for 8 hours at 40 ℃; heating the dried solid in a tubular heating furnace from room temperature (15-25 ℃) to 310 ℃ and preserving heat for 4 hours, then heating to 450 ℃ at the same heating rate and preserving heat for 4 hours to obtain the Ce composition0.8Mn0.1Zr0.1O2The prepared composite oxide has a three-dimensional ordered macroporous structure, and small molecular gas has no resistance in the macroporous structure and can directly and freely flow out through the macroporous structure.
Group C: similar to example 1, except that the additive was prepared according to a different method, the group prepared Ce — Zr two-dimensional oxide according to the following specific preparation method:
dissolving a certain amount of cerium nitrate and zirconium oxychloride (wherein the molar ratio of the cerium nitrate to the zirconium oxychloride is 1:1) in a mixed solution of absolute ethyl alcohol and methanol at a stirring speed of 200r/min, uniformly stirring at 25 ℃, then dropwise adding ammonia water into the solution, adjusting the pH to 9, continuously stirring for 2 hours, aging at room temperature for 24 hours under a vacuum condition after the stirring is finished, then carrying out suction filtration, and drying the obtained solid for 8 hours at 40 ℃; and (3) heating the dried solid in a muffle furnace from room temperature (15-25 ℃) to 550 ℃ and preserving heat for 4 hours to obtain the two-dimensional composite oxide of Ce-Zr.
Group D: similar to example 1, except that the additive was prepared by a different method, and this group prepared Mn — Zr two-dimensional oxides as follows:
under the stirring speed of 200r/min, dissolving a certain amount of manganese nitrate and zirconium oxychloride (wherein the molar ratio of the manganese nitrate to the zirconium oxychloride is 9:1) in a mixed solution of anhydrous methanol and distilled water, then uniformly stirring at 25 ℃, then dropwise adding ammonia water into the solution, adjusting the pH to 9, continuing stirring for 2 hours, aging under a vacuum condition at room temperature for 24 hours, then carrying out suction filtration, and drying the obtained solid in a vacuum drying oven at room temperature for 8 hours; and (3) heating the dried solid in a muffle furnace from room temperature (15-25 ℃) to 500 ℃ and preserving the temperature for 4 hours to obtain the two-dimensional composite oxide with the composition of Mn-Zr.
Group E: similar to example 1, except that the additive was prepared according to a different method, the group prepared Ce-Mn two-dimensional oxides according to the following specific preparation method:
dissolving a certain amount of cerium nitrate and manganese nitrate (wherein the molar ratio of ammonium cerium nitrate to manganese nitrate is 1:1) in a mixed solution of absolute ethyl alcohol and methanol at a stirring speed of 200r/min, uniformly stirring at 25 ℃, then dropwise adding ammonia water into the solution, adjusting the pH to 9, continuously stirring for 2 hours, aging at room temperature for 24 hours under a vacuum condition after the stirring is finished, then carrying out suction filtration, and drying the obtained solid for 8 hours at 40 ℃ in a vacuum drying oven; and (3) heating the dried solid in a muffle furnace from room temperature (15-25 ℃) to 550 ℃ and preserving heat for 4 hours to obtain the two-dimensional composite oxide of Ce-Mn.
The composite material obtained from the groups A to E is subjected to hydrogen absorption/desorption performance test by adopting the conventional test device and steps, and the specific test results are shown in the following table:
Figure BDA0003240126220000081
as can be seen from the above examples, the two-dimensional oxide pair MgH2The hydrogen absorption and desorption performances of the composite material have certain promotion effect, but the overall effect is not as obvious as that of three-dimension. Meanwhile, the structure has a large influence on the performance of the catalyst. In this example, the morphology of the three-dimensional Ce-Fe-Zr oxide prepared from group B has larger pores due to the three-dimensional ordered macroporous structure to MgH2The hydrogen absorption and desorption performance of (1) is inferior to that of Ce0.8Mn0.1Zr0.1O2This is mainly due to the fact that it is difficult to capture hydrogen atoms and catalyze them by the three-dimensional macroporous structure during the catalysis process, and hydrogen and the materialIn the process of contact, hydrogen gas has certain fluidity as a gas, is easy to escape through the material, is difficult to adhere to the surface of the material, and is difficult to catalyze effectively. The catalyst has a disordered structure, the appearance of the catalyst is shown in figure 7, and MgH is further treated due to the synergistic effect of Co/Mn, Zr and Ce in the catalytic process2Has obvious catalytic effect.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims (8)

1. The preparation method of the magnesium-based hydrogen storage composite material is characterized by comprising the following steps of:
(1)MgH2preparation of the Material
Putting a certain amount of Mg powder into a hydrogenation tube, reacting at 400 ℃ and 4Mpa hydrogen pressure to prepare MgH2A material;
(2) preparation of the additives
(21) Dissolving cerium salt in a mixed solvent of methanol and water, and after ultrasonic treatment and uniform mixing, marking the solution as A;
(22) dissolving zirconium oxychloride in a mixed solvent of ethylene glycol and water, and after ultrasonic treatment and uniform mixing, marking the solution as B;
(23) dissolving cobalt salt or manganese salt in deionized water, and marking the solution as C after ultrasonic treatment and uniform mixing;
(24) dropwise adding the solution B into the solution A at a dropwise adding rate of 0.1mL/s, uniformly mixing, continuously stirring for 2 hours to obtain a mixed solution, dropwise adding the solution C into the mixed solution, and stirring for 1 hour in a sealed manner to obtain a solution D;
(25) adding a surfactant into the solution D, continuously stirring for 30min after the surfactant is completely dissolved, then dropwise adding a precipitator into the solution, adjusting the pH value to be alkaline, continuously stirring for 2h, and aging for 24h under a vacuum condition at room temperature after the stirring is finished to obtain E;
(26) centrifuging the E, repeatedly washing the centrifuged product with deionized water and absolute ethyl alcohol for many times, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain F;
(27) placing the F in a muffle furnace for two-stage calcination, wherein the first stage calcination is performed by heating to 250 ℃ at room temperature and keeping the temperature for 2 hours, the second stage calcination is performed by heating to 600 ℃ from 250 ℃ and keeping the temperature for 5 hours, and cooling along with the furnace to room temperature to obtain the additive solid solution Ce0.8Co0.1Zr0.1O2Or Ce0.8Mn0.1Zr0.1O2A sample;
(3) ball milling preparation of composite material
MgH is added2And the additive is placed in a ball milling tank under the argon atmosphere, ball milling is carried out under the ball-material ratio of 20:1, the ball milling rotating speed is 350r/min, the ball milling is suspended for 15min every 30min, and the circulation is carried out for 10 times; and (4) taking out the ball milling tank after the ball milling is finished, and naturally cooling at room temperature to obtain the composite material.
2. The method as claimed in claim 1, wherein in step (21), the cerium salt is cerium nitrate hexahydrate or ammonium cerium nitrate.
3. The method of claim 1, wherein in step (23), the cobalt salt is cobalt nitrate hexahydrate, and the manganese salt is manganese sulfate.
4. The method of claim 1, wherein in step (25), said pH is between 9 and 11.
5. The method of claim 1, wherein in step (25), the surfactant is one of cetyltrimethylammonium bromide, ascorbic acid or citric acid.
6. The method as claimed in claim 1, wherein in step (25), the precipitant is ammonia water or sodium hydroxide solution.
7. The method of claim 1, wherein in step (2), the molar ratio of cerium salt, cobalt salt or manganese salt to zirconium oxychloride is 8:1: 1.
8. the method as claimed in any one of claims 1 to 7, wherein in step (27), the temperature increase rate of the first stage calcination is 2 ℃/min and the temperature increase rate of the second stage calcination is 1 ℃/min.
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MAYURANATH SURESH KUMAR等: "Study on Three-Way Catalytic Converters and the use of Oxides as Reduction and Oxidation", 《INTERNATIONAL JOURNAL OF ENGINEERING RESEARCH & TECHNOLOGY (IJERT)》 *

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