CN106179368A - The higher LaCoO with core-shell structure of a kind of catalytic performance3@La (OH)3composite catalyst and preparation method thereof - Google Patents
The higher LaCoO with core-shell structure of a kind of catalytic performance3@La (OH)3composite catalyst and preparation method thereof Download PDFInfo
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- CN106179368A CN106179368A CN201610587757.4A CN201610587757A CN106179368A CN 106179368 A CN106179368 A CN 106179368A CN 201610587757 A CN201610587757 A CN 201610587757A CN 106179368 A CN106179368 A CN 106179368A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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Abstract
The present invention discloses the higher LaCoO with core-shell structure of a kind of catalytic performance3@La(OH)3Composite catalyst and preparation method thereof, for electrostatic spinning alkali cleaning in-situ synthesis.It is characterized in that: described composite catalyst catalytic performance is higher that there is core-shell structure, La (OH)3For shell, Ca-Ti ore type LaCoO3For core.Described preparation method synthesizes Ca-Ti ore type LaCoO initially with method of electrostatic spinning3Nanofiber, then with strong base solution to LaCoO3Nanofiber carries out alkali cleaning process, is finally washed with deionized water alkali liquor, drying, obtains LaCoO3@La(OH)3Composite catalyst.Temperature needed for using the method to prepare catalyst is relatively low, saves the energy, and technique is simple, can improve the popularization and application of the catalytic performance of catalyst, beneficially perofskite type oxide.
Description
Technical field
The present invention relates to preparation and the application of a kind of perofskite type oxide composite catalyst, be specifically related to use Static Spinning
Silk technology and the combination of alkali cleaning, fabricated in situ has the LaCoO of core-shell structure3@La(OH)3Composite catalyst.
Background technology
A large amount of discharges of volatile organic matter (VOCs) can cause serious environmental pollution, both may be directly to health
Cause damage, it is also possible to be converted into photochemical fog or PM2.5, cause secondary pollution.Therefore the removal of VOCs is environmental conservation
One of great subject under discussion.Catalytic oxidation has that initiation temperature is low, saves the energy, applied widely, treatment effeciency is high and without two
The advantages such as secondary pollution, become main flow and developing direction that current VOCs administers.Noble metal catalyst has higher urging to VOCs
Change oxidability, but its resource scarcity, expensive, and heat stability is poor, research worker is devoted to select noble metal always
The succedaneum of catalyst.(formula is ABO to perofskite type oxide3) relatively inexpensive, form flexible and changeable, there is higher catalysis
Performance and thermal stability, be expected to become the succedaneum of noble metal catalyst, is current study hotspot.
But, the relatively low reason of perofskite type oxide catalytic performance limits its industrial applications.Specific surface area is low is
Cause the primary factor that perofskite type oxide catalytic performance is low, therefore, be an up Ca-Ti ore type oxygen by promoting specific surface area
One of compound catalytic performance effective way.End is got up, and research worker mainly promotes Ca-Ti ore type by three below approach
The reference area of oxide: (1) reduces crystallization temperature.The crystallization temperature reducing perofskite type oxide can suppress it effectively
The growth of crystal grain, so that perofskite type oxide keeps large specific surface area.(2) load method.Perofskite type oxide is born
It is loaded on the carrier with high specific surface area, it is possible to increase its dispersion, prevents high temperature sintering, thus promote its specific surface area
And catalytic performance.(3) novel method for synthesizing is used.As nanometer casting method and method of electrostatic spinning etc. can synthesize, there is special knot
The catalyst that structure, specific surface are higher, can be obviously improved the catalytic performance of perofskite type oxide.Perofskite type oxide is carried out
Structural modification is an up the another kind of effective ways of its catalytic performance.The most common method of modifying has: (1) metal ion replaces
Method.Perofskite type oxide (ABO3) catalysis activity depend primarily on B bit element, A/B bit element is carried out part replacement or
Replace, the electronic structure of B position ion can be changed, strengthen Oxygen mobility, and then promote the catalytic performance of perofskite type oxide；
(2) halogen doping.Research shows, by halide ion (F-Or Cl-) it is doped to ABO3Lattice in scalable B position cation each
Oxidation state ratio, increases the mobility of Lattice Oxygen, thus promotes the catalytic oxidation performance of perofskite type oxide.It addition, many groups
Point composite algorithm also can effectively promote perofskite type oxide catalytic performance.Research in recent years shows, is born by a small amount of noble metal
It is loaded in Ca-Ti ore type oxide surface, the noble metal obtained-perovskite composite catalyst, the catalysis of perovskite can not only be promoted
Performance, also has preferable stability.
Multicomponent composite algorithm is one of research direction of currently lifting perofskite type oxide catalytic performance.But report at present
More is noble metal-perovskite composite catalyst, and carrying method usually uses infusion process, it is understood that there may be active component is moved
The problems such as shifting, dispersion is poor, load factor is relatively low.
Summary of the invention
In view of the above problems, it is an object of the invention to provide that a kind of catalytic performance is higher has core-shell structure
LaCoO3@La(OH)3Composite catalyst and preparation method thereof electrostatic spinning-alkali cleaning in-situ synthesis, this method utilizes strong
Etching alkaline solution LaCoO3Nanofiber shows, in-situ preparation La (OH)3Crystal, forms the composite with core-shell structure, carries
Rise LaCoO3Catalytic oxidation performance.
Use technical scheme as follows for realizing the purpose of the present invention: a kind of catalytic performance is higher has core-shell structure
LaCoO3@La(OH)3Composite catalyst, it is characterised in that: described LaCoO3@La(OH)3Composite catalyst has higher urging
Change performance and special structural shell nuclear structure, La (OH)3For shell, Ca-Ti ore type LaCoO3For core.
The higher LaCoO with core-shell structure of a kind of catalytic performance of the present invention3@La(OH)3Composite catalyst, its
Be characterised by, following method preparing, it comprises the steps:
1) by Lanthanum (III) nitrate, cobalt nitrate, polyvinylpyrrolidone and citric acid are dissolved in N, N-dimethyl formyl by magnetic agitation
In amine solvent, prepare electrostatic spinning precursor solution；
2) method of electrostatic spinning is used by step 1) the electrostatic spinning precursor solution prepared makes composite nano fiber, then by it
8～15 h are preserved in being placed in exsiccator；
3) by step 2) composite nano fiber prepared is placed in Muffle furnace, calcines in air atmosphere, obtain perovskite
Type LaCoO3；
4) with strong base solution to step 3) the Ca-Ti ore type LaCoO for preparing3Carry out alkali cleaning, more supreme with deionized water centrifuge washing
Clear liquid is neutral, sample is finally dried at 70～90 DEG C 12～24 h, obtains LaCoO3@La(OH)3Composite catalyst.
In described electrostatic spinning precursor solution, lanthanum element is 1:1 with the ratio of the amount of cobalt element material, the total matter of nitrate
Amount (g) is 0.03～0.04:1 with volume (mL) ratio of solvent DMF, the amount of the citric acid material added
For 2～4 times of lanthanum element, polyvinylpyrrolidone quality (g) with volume (mL) ratio of solvent DMF is
0.07～0.12:1.
The higher LaCoO with core-shell structure of a kind of catalytic performance as claimed in claim 1 or 23@La(OH)3It is combined and urges
Agent, it is characterised in that: described electrostatic spinning voltage is 23 kV, and charging rate is 1.0 mL/h, and temperature is 43 DEG C, stainless
Draw point head internal diameter is 1 mm, and receiving range is 15 cm, and the lasting Electrospun time is 8～10 h.
The heating rate of composite nano fiber calcining is 2～8 DEG C/min, and calcining thermostat temperature is 500 DEG C, calcines constant temperature
Time is 4 h；Described strong base solution is NaOH solution or the KOH solution of brand-new, and concentration is 2～10 mol/L, LaCoO3's
Quality (g) is 0.004～0.01:1 with volume (mL) ratio of strong base solution；In alkaline cleaning procedure, solution constantly carries out magnetic force and stirs
Mixing, temperature controls at 50～80 DEG C, and the alkali cleaning time is 3～9 h, after alkali cleaning terminates, is washed away by alkali liquor with deionized water, until
Cleaning mixture is neutrality.
The higher LaCoO with core-shell structure of a kind of catalytic performance of the present invention3@La(OH)3The system of composite catalyst
Preparation Method, comprises the steps:
1) by Lanthanum (III) nitrate, cobalt nitrate, polyvinylpyrrolidone and citric acid are dissolved in N, N-dimethyl formyl by magnetic agitation
In amine solvent, prepare electrostatic spinning precursor solution；
2) method of electrostatic spinning is used by step 1) the electrostatic spinning precursor solution prepared makes composite nano fiber, then by it
8～15 h are preserved in being placed in exsiccator；
3) by step 2) composite nano fiber prepared is placed in Muffle furnace, calcines in air atmosphere, obtain perovskite
Type LaCoO3；
4) with strong base solution to step 3) the Ca-Ti ore type LaCoO for preparing3Carry out alkali cleaning, more supreme with deionized water centrifuge washing
Clear liquid is neutral, sample is finally dried at 70～90 DEG C 12～24 h, obtains LaCoO3@La(OH)3Composite catalyst.
Method as claimed in claim 6, it is characterised in that: in described electrostatic spinning precursor solution, lanthanum element with
The ratio of the amount of cobalt element material is 1:1, and nitrate gross mass (g) with volume (mL) ratio of solvent DMF is
0.03～0.04:1, amount is lanthanum element 2～4 times of the citric acid material added, polyvinylpyrrolidone quality (g) is with molten
Volume (mL) ratio of agent N,N-dimethylformamide is 0.07～0.12:1.
Described electrostatic spinning voltage is 23 kV, and charging rate is 1.0 mL/h, and temperature is 43 DEG C, in rustless steel syringe needle
Footpath is 1 mm, and receiving range is 15 cm, and the lasting Electrospun time is 8～10 h.
The heating rate of above-mentioned composite nano fiber calcining is 2～8 DEG C/min, and calcining thermostat temperature is 500 DEG C, calcining
Constant temperature time is 4 h；Described strong base solution is NaOH solution or the KOH solution of brand-new, and concentration is 2～10 mol/L,
LaCoO3Volume (mL) ratio of quality (g) and strong base solution be 0.004～0.01:1；In alkaline cleaning procedure, solution constantly enters
Row magnetic agitation, temperature controls at 50～80 DEG C, and the alkali cleaning time is 3～9 h, after alkali cleaning terminates, is washed by alkali liquor with deionized water
Go, until cleaning mixture is neutrality.
Specifically, the higher LaCoO with core-shell structure of a kind of catalytic performance of the present invention3@La(OH)3Compound
The preparation method of catalyst, comprises the steps:
(1) by Lanthanum (III) nitrate, cobalt nitrate, polyvinylpyrrolidone and citric acid are dissolved in N, N-dimethyl formyl by magnetic agitation
In amine solvent, prepare electrostatic spinning precursor solution；
(2) use method of electrostatic spinning that the electrostatic spinning precursor solution that step (1) is prepared is made composite nano fiber, then
8～15 h are preserved in being placed on exsiccator；
(3) composite nano fiber prepared by step (2) is placed in Muffle furnace, calcines in air atmosphere, obtain calcium titanium
Ore deposit type LaCoO3；
(4) the Ca-Ti ore type LaCoO with strong base solution prepared by step (3)3Carry out alkali cleaning, then with deionized water centrifuge washing extremely
Supernatant is neutral, sample is finally dried at 70～90 DEG C 12～24 h, obtains LaCoO3@La(OH)3Composite catalyst.
It is preferred that in electrostatic spinning precursor solution described in step (1), lanthanum element with the ratio of the amount of cobalt element material is
1:1, nitrate gross mass (g) is 0.03～0.04:1 with volume (mL) ratio of solvent DMF, is added
The amount of citric acid material is 2～4 times of lanthanum element, polyvinylpyrrolidone quality (g) and solvent DMF
Volume (mL) ratio is 0.07～0.12:1.
It is preferred that the electrostatic spinning voltage of step (2) is 23 kV, charging rate is 1.0 mL/h, and temperature is 43 DEG C, no
Rust draw point head internal diameter is 1 mm, and receiving range is 15 cm, and the lasting Electrospun time is 8～10 h.
It is preferred that the heating rate of step (3) composite nano fiber calcining is 2～8 DEG C/min, calcining thermostat temperature is
500 DEG C, calcining constant temperature time is 4 h；Strong base solution is NaOH solution or the KOH solution of brand-new, and concentration is 2～10 mol/L,
LaCoO3Volume (mL) ratio of quality (g) and strong base solution be 0.004～0.01:1；In alkaline cleaning procedure, solution constantly enters
Row magnetic agitation, temperature controls at 50～80 DEG C, and the alkali cleaning time is 3～9 h, after alkali cleaning terminates, is washed by alkali liquor with deionized water
Go, until cleaning mixture is neutrality.
From above-mentioned technical scheme it can be seen that there is advantages that
(1) LaCoO3@La(OH)3Composite catalyst has special microstructure core-shell structure, La (OH)3For shell, calcium
Titanium ore type LaCoO3For core, La (OH)3With Ca-Ti ore type LaCoO3Compound be effectively improved LaCoO3Catalytic performance；
(2) under the effect of highly basic, LaCoO3Nanofiber shows in-situ preparation La (OH)3, formed and there is core-shell structure
LaCoO3@La(OH)3The advantages such as composite catalyst, has technique simple, easy to operate.
Accompanying drawing explanation
Fig. 1 is the SEM figure TEM figure with non-alkali cleaning sample and the sample of alkali cleaning 9 h of each sample prepared by embodiment.
Fig. 2 is the XRD spectra of each sample prepared by embodiment.
Fig. 3 is the catalytic conversion figure at different temperatures to benzene of each sample prepared by embodiment.
Detailed description of the invention
For being best understood from the present invention, below in conjunction with embodiment, the present invention is described further, but application claims
The scope of protection is not limited to the scope that embodiment represents.
Embodiment
1) 0.3690 g La (NO is accurately weighed3)3·nH2O、0.3215 g Co(NO3)2·6H2O and 0.6965 g
C6H8O7·H2O (the wherein ratio La:Co:C of the amount of the material of lanthanum element, cobalt element and citric acid6H8O7=1:1:3.0) in 50 mL
Conical flask in, and add 2.000 g PVP and 20 mL DMF solution, at room temperature, magnetic agitation, to being completely dissolved, obtains
In mauve, homogeneous electrostatic spinning precursor solution.
2) to step 1) the electrostatic spinning precursor solution prepared carries out electrostatic spinning, and condition is: feed liquor speed 1.0 mL/
H, voltage 23.0 kV, temperature 43 DEG C, rustless steel syringe needle internal diameter 1 mm, receiving range 15 cm, the electrostatic spinning persistent period is 10
h.After electrostatic spinning terminates, obtain composite nano fiber, be placed on room temperature preservation 12 h in exsiccator.
3) by step 2) composite nano fiber that obtains, it is placed in crucible, puts in Muffle furnace and calcine.With 5 DEG C/min's
Heating rate rises to 500 DEG C from room temperature, calcining at constant temperature 4 h, obtains Ca-Ti ore type LaCoO3。
4) 0.20 g step 3 is weighed) the Ca-Ti ore type LaCoO that obtains34 parts of sample, being separately added into 50 ml concentration is 2 M
NaOH solution (new preparation), the water-bath of 60 DEG C is stirred 3h, 5h, 7h and 9 h respectively, be then centrifuged for, outwell supernatant
Liquid, by distilled water repeatedly washing sample, until solution supernatant is neutrality.Sample washed for distilled water is placed in baking oven 80
DEG C dry 12 h, obtain final electrostatic spinning-alkali cleaning fabricated in situ and there is the LaCoO of core-shell structure3@La(OH)3Composite catalyzing
Agent sample.
Fig. 1 is the TEM figure of sample after the SEM figure of embodiment each sample prepared and non-alkali cleaning sample and alkali cleaning 9 h.From
SEM figure can be seen that random arrangement before the composite fiber calcining that electrostatic spinning obtains, smooth surface, fiber seriality
Good, diameter is between 200-400 nm；After calcining, fibre diameter there occurs phenomenon of rupture, in the range of being contracted to 100-250 nm；
After sample NaOH solution processes the different time (3 h, 5 h, 7 h and 9 h), fiber surface has grown " fine hair shape " material.
The relatively TEM figure of the sample of non-alkali cleaning sample and alkali cleaning 9 h, it can be seen that the sample fiber of non-alkali cleaning piled up by nano-particle and
Becoming, after alkali cleaning 9 h, there is a lot " fold " (being " fine hair shape " material that SEM observes) in fiber surface.
Fig. 2 is the XRD spectra of each sample prepared by embodiment.It can be seen that non-alkali cleaning LaCoO3Sample
XRD goes out peak position () and can be well matched with standard card (JCPDS No.18-0123), for the LaCoO of oblique hexagonal crystal system3。
And the sample (3 h, 5 h and 7 h) after alkali cleaning is in 2 θ=15.6°, 27.2°, 28.0°With 39.4°Place (●) occurs in that hexagonal phase La
(OH)3Diffraction maximum (JCPDS No. 01-083-2034), it can thus be appreciated that alkali cleaning can dissolve LaCoO3The A position shape of nanofiber
Become La (OH)3。
XRD Yu SEM result illustrates LaCoO3Nanofiber surface after alkali cleaning processes, Surface Creation " fine hair shape "
Material is La (OH)3, define the LaCoO with core-shell structure3@La(OH)3Composite catalyst.
Fig. 3 is the catalytic conversion at different temperatures to benzene of each sample prepared by embodiment.By the most permissible
Find, the catalyst LaCoO obtained after alkali cleaning3@La(OH)3Composite catalyst catalytic performance and single Ca-Ti ore type
LaCoO3Compare the raising all having in various degree.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to the present patent application protection domain with
Modify, all should belong to the covering scope of the present invention.
Claims (9)
1. the higher LaCoO with core-shell structure of catalytic performance3@La(OH)3Composite catalyst, it is characterised in that: described
LaCoO3@La(OH)3Composite catalyst has higher catalytic performance and special structural shell nuclear structure, La (OH)3For
Shell, Ca-Ti ore type LaCoO3For core.
The higher LaCoO with core-shell structure of a kind of catalytic performance the most as claimed in claim 13@La(OH)3Composite catalyst,
It is characterized in that, following method preparing, it comprises the steps:
Lanthanum (III) nitrate, cobalt nitrate, polyvinylpyrrolidone and citric acid are dissolved in DMF by magnetic agitation
In solvent, prepare electrostatic spinning precursor solution；
Use method of electrostatic spinning that the electrostatic spinning precursor solution that step (1) is prepared is made composite nano fiber, then by it
8～15 h are preserved in being placed in exsiccator；
Composite nano fiber prepared by step (2) is placed in Muffle furnace, calcines in air atmosphere, obtain Ca-Ti ore type
LaCoO3；
The Ca-Ti ore type LaCoO with strong base solution prepared by step (3)3Carry out alkali cleaning, then with deionized water centrifuge washing to supernatant
Liquid is neutral, sample is finally dried at 70～90 DEG C 12～24 h, obtains LaCoO3@La(OH)3Composite catalyst.
The higher LaCoO with core-shell structure of a kind of catalytic performance the most as claimed in claim 1 or 23@La(OH)3Composite catalyzing
Agent, it is characterised in that: in described electrostatic spinning precursor solution, lanthanum element is 1:1 with the ratio of the amount of cobalt element material, nitric acid
Salt gross mass (g) is 0.03～0.04:1 with volume (mL) ratio of solvent DMF, the citric acid thing added
The amount of matter is 2～4 times of lanthanum element, polyvinylpyrrolidone quality (g) and the volume (mL) of solvent DMF
Ratio is 0.07～0.12:1.
The higher LaCoO with core-shell structure of a kind of catalytic performance the most as claimed in claim 1 or 23@La(OH)3Composite catalyzing
Agent, it is characterised in that: described electrostatic spinning voltage is 23 kV, and charging rate is 1.0 mL/h, and temperature is 43 DEG C, rustless steel
Syringe needle internal diameter is 1 mm, and receiving range is 15 cm, and the lasting Electrospun time is 8～10 h.
The higher LaCoO with core-shell structure of a kind of catalytic performance the most as claimed in claim 1 or 23@La(OH)3Composite catalyzing
Agent, it is characterised in that: the heating rate of composite nano fiber calcining is 2～8 DEG C/min, and calcining thermostat temperature is 500 DEG C, forges
Burning constant temperature time is 4 h；Described strong base solution is NaOH solution or the KOH solution of brand-new, and concentration is 2～10 mol/L,
LaCoO3Volume (mL) ratio of quality (g) and strong base solution be 0.004～0.01:1；In alkaline cleaning procedure, solution constantly enters
Row magnetic agitation, temperature controls at 50～80 DEG C, and the alkali cleaning time is 3～9 h, after alkali cleaning terminates, is washed by alkali liquor with deionized water
Go, until cleaning mixture is neutrality.
6. the higher LaCoO with core-shell structure of catalytic performance3@La(OH)3The preparation method of composite catalyst, including such as
Lower step:
Lanthanum (III) nitrate, cobalt nitrate, polyvinylpyrrolidone and citric acid are dissolved in DMF by magnetic agitation
In solvent, prepare electrostatic spinning precursor solution；
Use method of electrostatic spinning that the electrostatic spinning precursor solution that step (1) is prepared is made composite nano fiber, then by it
8～15 h are preserved in being placed in exsiccator；
Composite nano fiber prepared by step (2) is placed in Muffle furnace, calcines in air atmosphere, obtain Ca-Ti ore type
LaCoO3；
The Ca-Ti ore type LaCoO with strong base solution prepared by step (3)3Carry out alkali cleaning, then with deionized water centrifuge washing to supernatant
Liquid is neutral, sample is finally dried at 70～90 DEG C 12～24 h, obtains LaCoO3@La(OH)3Composite catalyst.
7. method as claimed in claim 6, it is characterised in that: in described electrostatic spinning precursor solution, lanthanum element and cobalt
The ratio of the amount of elemental substance is 1:1, and nitrate gross mass (g) is 0.03 with volume (mL) ratio of solvent DMF
～0.04:1, amount is lanthanum element 2～4 times of the citric acid material added, polyvinylpyrrolidone quality (g) and solvent N,
Volume (mL) ratio of dinethylformamide is 0.07～0.12:1.
Method the most as claimed in claims 6 or 7, it is characterised in that: described electrostatic spinning voltage is 23 kV, charging rate
Being 1.0 mL/h, temperature is 43 DEG C, and rustless steel syringe needle internal diameter is 1 mm, and receiving range is 15 cm, and the lasting Electrospun time is 8
～10 h.
Method the most as claimed in claims 6 or 7, it is characterised in that: the heating rate of composite nano fiber calcining is 2～8
DEG C/min, calcining thermostat temperature is 500 DEG C, and calcining constant temperature time is 4 h；Described strong base solution is the NaOH solution of brand-new
Or KOH solution, concentration is 2～10 mol/L, LaCoO3Quality (g) and strong base solution volume (mL) than be 0.004～
0.01:1；In alkaline cleaning procedure, solution constantly carries out magnetic agitation, and temperature controls at 50～80 DEG C, and the alkali cleaning time is 3～9
H, after alkali cleaning terminates, washes away alkali liquor with deionized water, until cleaning mixture is neutrality.
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| CN110184682A (en) * | 2019-05-31 | 2019-08-30 | 福建师范大学 | It is a kind of to prepare Ca-Ti ore type LaCoO3Low temperature calcination method |
| JP2020507452A (en) * | 2017-02-02 | 2020-03-12 | 本田技研工業株式会社 | Core shell |
| CN111389411A (en) * | 2019-01-03 | 2020-07-10 | 天津大学 | Perovskite electrocatalyst and preparation method and application thereof |
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| CN112582626A (en) * | 2020-12-22 | 2021-03-30 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Method for improving electrocatalytic activity of perovskite oxide and substance thereof |
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