CN105107520A - Double perovskite type metal oxide catalyst and preparation method thereof - Google Patents
Double perovskite type metal oxide catalyst and preparation method thereof Download PDFInfo
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Abstract
Relating to the technical field of catalysts, the invention discloses a double perovskite type metal oxide catalyst and a preparation method thereof to solve the problems of low catalytic activity and poor high-temperature stability o existing LaMnO3. The general formula of the double perovskite type metal oxide catalyst is: La1-xMxD1-yMnyO3, wherein x=0-0.6, y=0.7-1, M is alkali metal ion or alkaline earth metal ion, and D is +1, +2 or +3 valence metal ion. According to the double perovskite type metal oxide catalyst provided by the invention, the M ion and D ion are introduced to adjust the composition and structure of the perovskite metal oxide and increase the specific surface area, thereby enhancing the catalytic activity and high temperature stability of the catalyst. The catalyst provided by the invention is mainly applied to catalytic combustion of methane.
Description
Technical field
The present invention relates to catalyst technical field, particularly relate to a kind of double-perovskite type metal oxide catalyst and preparation method thereof.
Background technology
Along with the pay attention to day by day to the problem such as energy shortage and environmental pollution, the clean and efficient utilization of the energy is more and more subject to concern and the attention of society.Wherein, methane as the main component of the petroleum resourceses such as natural gas, shale gas and combustible ice, the focus that its effective utilization is paid close attention to especially.The catalytic combustion of methane as a kind of novel methyl hydride combustion technology, because its efficiency is high and avoid NO
xthe formation of the environmental contaminants such as (nitrogen oxide) and CO (carbon monoxide), become the hot research direction in this field, and catalyst is as the critical material research emphasis especially of the catalytic combustion of methane.
At present, because perovskite type metal oxide catalyst has certain superiority in heat endurance, chemical stability and structural stability, be therefore widely used in the catalytic combustion of methane.The general formula of perovskite type metal oxide catalyst is ABO
3, usual A is rare earth metal, and B is transition metal; Such as LaMnO
3(lanthanum manganate), LaMnO
3(lanthanum manganate) has the advantages such as preparation method is simple, cheap, therefore more and more receives the concern of researcher.
But present inventor finds: due to LaMnO
3the catalytic activity of catalyst depends on Mn in catalyst
3+the Mn that ion and crystal structure defects are formed
4+the oxidation of ion, and LaMnO
3in the Mn that formed by crystal defect
4+ion concentration is low, and the oxidability of manganese ion is poor, thus causes LaMnO
3catalytic activity lower.
Summary of the invention
The object of the present invention is to provide a kind of double-perovskite type metal oxide catalyst, for solving existing LaMnO
3the problem of catalytic activity low and high temperature poor stability.
For achieving the above object, the present invention adopts following technical scheme:
A kind of double-perovskite type metal oxide catalyst, the general formula of described double-perovskite type metal oxide catalyst is: La
1-xm
xd
1-ymn
yo
3, wherein, x=0 ~ 0.6, y=0.7 ~ 1, M is alkali metal ion or alkaline-earth metal ions, and D is+1 valency ,+divalent or+3 valence metal ions.
In double-perovskite type metal oxide catalyst provided by the invention, by the introducing of M ion and D ion, adjust to some extent with the component and structure that make perovskite metal oxide.On the one hand, the introducing of M ion and D ion can improve the specific area of catalyst, part Manganic ion can be made to generate tetravalent manganese ion simultaneously, improve the oxidability of manganese ion, and be conducive to forming reversible oxidation-reduction process between different valence state manganese ion, thus improve the catalytic performance of catalyst; On the other hand, after introducing D ion elements, due to D
+and D
2+or D
2+and D
3+reversible ionic process, and the synergy of D, Mn double ion, also can improve the catalytic activity of catalyst.
Another object of the present invention is to the preparation method that a kind of double-perovskite type metal oxide catalyst is provided, for solving existing LaMnO
3the problem of catalytic activity low and high temperature poor stability.For achieving the above object, the present invention adopts following technical scheme:
A preparation method for double-perovskite type metal oxide catalyst, comprising: mixed with precipitant solution by metal salt solution, and reaction generates containing sedimentary mixed liquor, isolates sediment from described containing sedimentary mixed liquor; Described sediment is dispersed in water or alcohols solvent, is precipitated thing suspension; Plus acidic solution in described precipitate suspension, the pH value regulating described precipitate suspension is 2 ~ 8, obtains containing described sedimentary mixed system, is left standstill by described mixed system, filters, and washing and filtering product; By the described filtration product calcining after washing, then cooling obtains double-perovskite type metal oxide catalyst.
In the preparation method of double-perovskite type metal oxide catalyst provided by the invention, due to by sediment being dispersed in water or alcohols solvent, be precipitated thing suspension, and acid solution is dripped in precipitate suspension, the pH value regulating precipitate suspension is 2 ~ 8, obtain containing sedimentary mixed system, this is contained sedimentary mixed system to leave standstill, filter, and washing and filtering product, therefore, it is possible to regulate and control the diauxic growth of catalyst particle, thus enable catalyst forming section or whole nanometer rods, because the micron ball of nanometer rods composition has higher specific area than the molecular micron ball of nanoparticle, therefore the specific area of catalyst is increased, make it have higher catalytic activity.
Accompanying drawing explanation
The flow chart of the preparation method of a kind of double-perovskite type metal oxide catalyst that Fig. 1 provides for the embodiment of the present invention;
The flow chart of the preparation method of the another kind of double-perovskite type metal oxide catalyst that Fig. 2 provides for the embodiment of the present invention.
Detailed description of the invention
For the ease of understanding, below in conjunction with Figure of description, double-perovskite type metal oxide catalyst that the embodiment of the present invention provides and preparation method thereof is described in detail.
The embodiment of the present invention provides a kind of double-perovskite type metal oxide catalyst, and the general formula of described double-perovskite type metal oxide catalyst is: La
1-xm
xd
1-ymn
yo
3, wherein, x=0 ~ 0.6, y=0.7 ~ 1, M is alkali metal ion or alkaline-earth metal ions, and D is+1 valency ,+divalent or+3 valence metal ions.
In the double-perovskite type metal oxide catalyst that the embodiment of the present invention provides, by the introducing of M ion and D ion, adjust to some extent with the component and structure that make perovskite metal oxide.On the one hand, the introducing of M ion and D ion can improve the specific area of catalyst, part Manganic ion can be made to generate tetravalent manganese ion simultaneously, improve the oxidability of manganese ion, and be conducive to forming reversible oxidation-reduction process between different valence state manganese ion, thus improve the catalytic performance of catalyst; On the other hand, after introducing D ion elements, due to D
+and D
2+or D
2+and D
3+reversible ionic process, and the synergy of D, Mn double ion, also can improve the catalytic activity of catalyst.
Wherein, in order to make double-perovskite type metal oxide catalyst have preferably catalytic activity and high-temperature stability, above-mentioned La further
1-xm
xd
1-ymn
yo
3the ionic radius scope of middle D ion can be
x can be 0.4, y can be 0.8, M ion can be Sr
2+, D ion can be Cu
2+, namely above-mentioned double-perovskite type metal oxide catalyst can be preferably La
0.6sr
0.4cu
0.2mn
0.8o
3.
Certainly, at above-mentioned La
1-xm
xd
1-ymn
yo
3in, x also can be 0.2 or 0.4, y also can be 0.8 or 0.9.
Particularly, above-mentioned double-perovskite type metal oxide catalyst can be um porous ball shape catalyst, this um porous ball shape catalyst can be piled up by nanometer rods and nano particle and be formed, thus the shortcoming of catalyst at high temperature easy-sintering reunion can be solved, further increase the high-temperature stability of catalyst.
The embodiment of the present invention also provides a kind of preparation method of double-perovskite type metal oxide catalyst, as shown in Figure 1, comprising:
Step S1, mixed with precipitant solution by metal salt solution, reaction generates containing sedimentary mixed liquor, isolates sediment from containing sedimentary mixed liquor; Wherein, metal salt solution can be one or more in nitrate solution, acetate solution, HCI solution or sulfate liquor, precipitant solution can be the precipitant solution of hydroxyl-containing ion or carbanion, such as ammonia spirit or sodium hydroxide solution; The reaction condition mixed with precipitant solution by metal salt solution can be: reaction temperature is 0 ~ 40 DEG C, such as 20 DEG C or 30 DEG C; The concentration of metal salt solution is 1 ~ 5mol/L, such as 3mol/L or 4mol/L; The concentration of precipitant solution is 0.1 ~ 5mol/L, is preferably 1 ~ 5mol/L, such as 3mol/L or 4mol/L.
Solvent in above-mentioned metal salt solution and precipitant solution is not limited, as long as slaine and precipitating reagent can be dissolved, is preferably water or alcohol.
Step S2, sediment to be dispersed in water or alcohols solvent, to be precipitated thing suspension; Wherein, the concentration of precipitate suspension is 0.01 ~ 1mol/L, such as 0.05mol/L, 0.1mol/L, 0.5mol/L or 1mol/L; The temperature of precipitate suspension is 25 ~ 80 DEG C, is preferably 40 ~ 60 DEG C, such as 45 DEG C or 55 DEG C.
Step S3, in precipitate suspension Plus acidic solution, regulate the pH value of precipitate suspension to be 2 ~ 8, obtain containing sedimentary mixed system, will, filtration standing containing sedimentary mixed system, and wash filtration product with water; Wherein, acid solution can be one or more in acetum, salpeter solution, acetic acid solution or hydrochloric acid solution, and regulate the pH value of precipitate suspension to be preferably 3 ~ 6, such as pH value is 4 or 5.
Solvent in above-mentioned acid solution is not limited, is preferably water.
Step S4, by washing after filtration product calcining, then cooling obtain double-perovskite type metal oxide catalyst.
In the preparation method of the double-perovskite type metal oxide catalyst that the embodiment of the present invention provides, due to by sediment being dispersed in water or alcohols solvent, be precipitated thing suspension, and acid solution is dripped in precipitate suspension, the pH value regulating precipitate suspension is 2 ~ 8, obtain containing sedimentary mixed system, this is contained sedimentary mixed system to leave standstill, filter, and washing and filtering product, therefore, it is possible to regulate and control the diauxic growth of catalyst particle, thus enable catalyst forming section or whole nanometer rods, because the micron ball of nanometer rods composition has higher specific area than the molecular micron ball of nanoparticle, therefore the specific area of catalyst is increased, make it have higher catalytic activity.
The embodiment of the present invention also provides the preparation method of another kind of double-perovskite type metal oxide catalyst, as shown in Figure 2, can also comprise between above-mentioned steps S3 and step S4:
Step S31, by washing after filtration product mix with the pore creating material aqueous solution or pore creating material alcoholic solution, ball milling, obtain slurries; Wherein, pore creating material can be one or more in starch, polyethylene glycol or PVP.
Step S32, mist projection granulating is carried out to slurries, obtain spherical catalyst particles; Wherein, the condition of mist projection granulating can be: the temperature of the air inlet of spray dryer is 150 ~ 250 DEG C, such as 175 DEG C, 215 DEG C or 245 DEG C; The temperature of air outlet is 100 ~ 150 DEG C, such as 105 DEG C, 125 DEG C or 145 DEG C; The flow velocity of peristaltic pump is 1 ~ 10mL/min, such as 2mL/min, 5mL/min, 6mL/min or 9mL/min; The wind speed of blower fan is 0.5 ~ 5m
3/ min, such as 0.8m
3/ min, 1.5m
3/ min, 3m
3/ min or 4m
3/ min.
In the preparation method of the another kind of double-perovskite type metal oxide catalyst that the embodiment of the present invention provides, owing to adding spray drying process prilling, part or all of nanometer rods can be made to form micron ball further, therefore solve the shortcoming that easy-sintering is reunited under catalyst high temperature, thus make it have higher high-temperature stability.
Enumerate the preparation method of two preferred embodiments to the double-perovskite type metal oxide catalyst that the embodiment of the present invention provides below to carry out specifically, explain.
Embodiment one:
Step S1, configuration concentration are that the nitrate aqueous solution of 1 ~ 5mol/L or acetate aqueous solution are as aqueous metal salt, configuration concentration is that the ammonia spirit of 1 ~ 5mol/L is as the precipitating reagent aqueous solution, aqueous metal salt and precipitating reagent aqueous solution equal-volume are mixed rapidly, carries out rapidly to enable reaction and generate sediment.More nucleus can be generated rapidly like this, the particle diameter of catalyst be reduced, thus obtains the catalyst material of high-specific surface area.Meanwhile, control course of reaction and carry out under the environment of 0 ~ 40 DEG C, lower temperature can suppress the growth rate of nucleus, promotes the generating rate of nucleus.
Step S2, the sediment generated in above-mentioned steps S1 to be dispersed in water or alcohols solvent, to be precipitated thing suspension.Wherein, the concentration controlling precipitate suspension is 0.01 ~ 1mol/L, and temperature is 40 ~ 60 DEG C.
Drip aqueous acetic acid in step S3, the precipitate suspension that generates in above-mentioned steps S2, the pH value regulating precipitate suspension is 3 ~ 6, stirs after 2 ~ 4 minutes, standing 2 ~ 24 hours, then filters, and washs filtration product by massive laundering.
Step S31, the filtration product will generated in above-mentioned steps S3, the pore creating material aqueous solution made with starch or alcoholic solution mix and blend, then ball milling 0.5 ~ 2 hour, obtains the slurries of stable homogeneous.Wherein, the consumption of pore creating material is 0.5% ~ 20%, and the consumption of pore creating material can be the weight ratio of filtration product and pore creating material.
Step S32, mist projection granulating is carried out to the slurries spray dryer generated in above-mentioned steps S31, obtain spherical catalyst particles.Wherein, by adjustment device parameter, the spherical catalyst particles that particle diameter is 1 ~ 40 micron can be obtained.Particularly, the condition of mist projection granulating can be: the temperature of the air inlet of spray dryer is set as 190 ~ 210 DEG C, the temperature of air outlet is set as 100 ~ 120 DEG C, and the flow rate set of peristaltic pump is 4 ~ 8mL/min, and the wind speed of blower fan is set as 1 ~ 2m
3/ min.
Step S4, the spherical catalyst particles generated in above-mentioned steps S32 is put into Muffle furnace high-temperature calcination, 600 ~ 1000 DEG C are warming up to by the speed of 2 DEG C/min, be incubated 2 ~ 5 hours, then the powder body material of double-perovskite type metal oxide catalyst can be obtained after naturally cooling.
Embodiment two:
Step S1, configuration concentration are that the nitrate aqueous solution of 1 ~ 5mol/L or acetate aqueous solution are as aqueous metal salt, configuration concentration is that the sodium hydroxide solution of 1 ~ 5mol/L is as the precipitating reagent aqueous solution, aqueous metal salt is added drop-wise in the precipitating reagent aqueous solution, generates sediment.Metal ion instant precipitation simultaneously can be made like this, generate more nucleus, the particle diameter of catalyst is reduced, thus obtains the catalyst material of high-specific surface area.Meanwhile, control course of reaction and carry out under the environment of 0 ~ 40 DEG C, lower temperature can suppress the growth rate of nucleus, promotes the generating rate of nucleus.
Step S2, the sediment generated in above-mentioned steps S1 to be dispersed in water or alcohols solvent, to be precipitated thing suspension.Wherein, the concentration controlling precipitate suspension is 0.01 ~ 1mol/L, and temperature is 40 ~ 60 DEG C.
Drip aqueous solution of nitric acid in step S3, the precipitate suspension that generates in above-mentioned steps S2, the pH value regulating precipitate suspension is 3 ~ 6, stirs after 2 ~ 4 minutes, standing 2 ~ 24 hours, then filters, and washs filtration product by massive laundering.
Step S31, the filtration product will generated in above-mentioned steps S3, mix with a certain amount of water and stir, the concentration of the suspension now containing filtration product can be 5% ~ 80%, is preferably 10% ~ 40%, then ball milling 0.5 ~ 2 hour, obtains the slurries of stable homogeneous.
Step S32, mist projection granulating is carried out to the slurries spray dryer generated in above-mentioned steps S31, obtain spherical catalyst particles.Wherein, by adjustment device parameter, the spherical catalyst particles that particle diameter is 1 ~ 40 micron can be obtained.Particularly, the condition of mist projection granulating can be: the temperature of the air inlet of spray dryer is set as 190 ~ 210 DEG C, the temperature of air outlet is set as 100 ~ 120 DEG C, and the flow rate set of peristaltic pump is 4 ~ 8mL/min, and the wind speed of blower fan is set as 1 ~ 2m
3/ min.
Step S4, the spherical catalyst particles generated in above-mentioned steps S32 is put into Muffle furnace high-temperature calcination, 600 ~ 1000 DEG C are warming up to by the speed of 2 DEG C/min, be incubated 2 ~ 5 hours, then the powder body material of double-perovskite type metal oxide catalyst can be obtained after naturally cooling.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; change can be expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of described claim.
Claims (12)
1. a double-perovskite type metal oxide catalyst, is characterized in that, the general formula of described double-perovskite type metal oxide catalyst is: La
1-xm
xd
1-ymn
yo
3, wherein, x=0 ~ 0.6, y=0.7 ~ 1, M is alkali metal ion or alkaline-earth metal ions, and D is+1 valency ,+divalent or+3 valence metal ions.
2. double-perovskite type metal oxide catalyst according to claim 1, is characterized in that, described M ion is Sr
2+, described D ion is Cu
2+.
3. double-perovskite type metal oxide catalyst according to claim 2, is characterized in that, described x is 0.4, described y is 0.8.
4. double-perovskite type metal oxide catalyst according to claim 1, it is characterized in that, described double-perovskite type metal oxide catalyst is um porous ball shape catalyst, and described um porous ball shape catalyst is piled up by nanometer rods and nano particle and formed.
5. a preparation method for double-perovskite type metal oxide catalyst, is characterized in that, comprising:
Mixed with precipitant solution by metal salt solution, reaction generates containing sedimentary mixed liquor, isolates sediment from described containing sedimentary mixed liquor;
Described sediment is dispersed in water or alcohols solvent, is precipitated thing suspension;
Plus acidic solution in described precipitate suspension, the pH value regulating described precipitate suspension is 2 ~ 8, obtains containing described sedimentary mixed system, is left standstill by described mixed system, filters, and washing and filtering product;
By the described filtration product calcining after washing, then cooling obtains double-perovskite type metal oxide catalyst.
6. the preparation method of double-perovskite type metal oxide catalyst according to claim 4, is characterized in that, by the described filtration product calcining after washing, then cooling obtain the step of double-perovskite type metal oxide catalyst before also comprise:
By washing after described filtration product mix with the pore creating material aqueous solution or pore creating material alcoholic solution, ball milling, obtain slurries;
Mist projection granulating is carried out to described slurries, obtains spherical catalyst particles.
7. the preparation method of double-perovskite type metal oxide catalyst according to claim 5, is characterized in that, described pore creating material is one or more in starch, polyethylene glycol or PVP.
8. the preparation method of double-perovskite type metal oxide catalyst according to claim 5, it is characterized in that, the condition of described mist projection granulating is: the temperature of the air inlet of spray dryer is 150 ~ 250 DEG C, the temperature of air outlet is 100 ~ 150 DEG C, the flow velocity of peristaltic pump is 1 ~ 10mL/min, and the wind speed of blower fan is 0.5 ~ 5m
3/ min.
9. the preparation method of double-perovskite type metal oxide catalyst according to claim 4, is characterized in that, described metal salt solution is one or more in nitrate solution, acetate solution, HCI solution or sulfate liquor;
Described precipitant solution is the precipitant solution of hydroxyl-containing ion or carbanion.
10. the preparation method of double-perovskite type metal oxide catalyst according to claim 4, it is characterized in that, described metal salt solution to be mixed with precipitant solution, the reaction condition that reaction generates containing sedimentary mixed liquor is: reaction temperature is 0 ~ 40 DEG C, the concentration of described metal salt solution is 1 ~ 5mol/L, and the concentration of described precipitant solution is 0.1 ~ 5mol/L.
The preparation method of 11. double-perovskite type metal oxide catalysts according to claim 4, is characterized in that, the concentration of described precipitate suspension is 0.01 ~ 1mol/L, and the temperature of described precipitate suspension is 25 ~ 80 DEG C.
The preparation method of 12. double-perovskite type metal oxide catalysts according to claim 4, is characterized in that, described acid solution is one or more in acetum, salpeter solution, acetic acid solution or hydrochloric acid solution.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728063A (en) * | 2016-03-23 | 2016-07-06 | 新奥科技发展有限公司 | Preparation method of metal substrate catalyst |
| CN106475105A (en) * | 2016-08-26 | 2017-03-08 | 西安交通大学 | A kind of double-perovskite type O composite metallic oxide catalyst and preparation method and application |
| CN107285383A (en) * | 2017-06-29 | 2017-10-24 | 宁波吉电鑫新材料科技有限公司 | A kind of one-step synthesis double-perovskite kalium ion battery negative material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867966A (en) * | 2012-09-29 | 2013-01-09 | 南开大学 | Porous micro-sphere post-spinel nitride calcium manganese oxygen compound, and preparation of and application thereof |
| CN102989448A (en) * | 2012-12-18 | 2013-03-27 | 天津大学 | Preparation method and application of lanthanum-manganese perovskite type NOx removing catalyst |
| CN103165876A (en) * | 2011-12-15 | 2013-06-19 | 新奥科技发展有限公司 | A preparation method and applications of a lithium battery material with high rate performance |
| CN103199269A (en) * | 2013-03-21 | 2013-07-10 | 上海交通大学 | Preparation method of functional gradient cathode of intermediate low temperature solid oxide fuel cell |
-
2015
- 2015-07-21 CN CN201510430347.4A patent/CN105107520B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165876A (en) * | 2011-12-15 | 2013-06-19 | 新奥科技发展有限公司 | A preparation method and applications of a lithium battery material with high rate performance |
| CN102867966A (en) * | 2012-09-29 | 2013-01-09 | 南开大学 | Porous micro-sphere post-spinel nitride calcium manganese oxygen compound, and preparation of and application thereof |
| CN102989448A (en) * | 2012-12-18 | 2013-03-27 | 天津大学 | Preparation method and application of lanthanum-manganese perovskite type NOx removing catalyst |
| CN103199269A (en) * | 2013-03-21 | 2013-07-10 | 上海交通大学 | Preparation method of functional gradient cathode of intermediate low temperature solid oxide fuel cell |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728063A (en) * | 2016-03-23 | 2016-07-06 | 新奥科技发展有限公司 | Preparation method of metal substrate catalyst |
| CN105728063B (en) * | 2016-03-23 | 2018-06-12 | 新奥科技发展有限公司 | A kind of preparation method of metal substrate catalyst |
| CN106475105A (en) * | 2016-08-26 | 2017-03-08 | 西安交通大学 | A kind of double-perovskite type O composite metallic oxide catalyst and preparation method and application |
| CN106475105B (en) * | 2016-08-26 | 2019-02-05 | 西安交通大学 | A kind of double-perovskite type O composite metallic oxide catalyst and the preparation method and application thereof |
| CN107285383A (en) * | 2017-06-29 | 2017-10-24 | 宁波吉电鑫新材料科技有限公司 | A kind of one-step synthesis double-perovskite kalium ion battery negative material and preparation method thereof |
| CN108714426A (en) * | 2018-06-15 | 2018-10-30 | 武汉理工大学 | A kind of nanocube perovskite type catalyst and its preparation method and application |
| CN109939747A (en) * | 2019-04-24 | 2019-06-28 | 南京威安新材料科技有限公司 | A kind of preparation facilities and method of the support type perovskite catalyst for oxidative degradation organic-fuel |
| CN109939747B (en) * | 2019-04-24 | 2023-10-03 | 南京威安新材料科技有限公司 | Preparation device and method of supported perovskite catalyst for oxidative degradation of organic fuel |
| CN115353149A (en) * | 2022-09-01 | 2022-11-18 | 中国计量大学 | Perovskite manganese oxide porous nanosphere and preparation method and application thereof |
| CN115353149B (en) * | 2022-09-01 | 2023-09-15 | 中国计量大学 | Perovskite manganese oxide porous nanosphere and preparation method and application thereof |
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