CN107673411A - A kind of preparation method of the mesoporous perovskite oxide of macropore - Google Patents
A kind of preparation method of the mesoporous perovskite oxide of macropore Download PDFInfo
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- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1264—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing rare earth, e.g. La1-xCaxMnO3, LaMnO3
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Abstract
The invention discloses a kind of preparation method of the mesoporous perovskite oxide of macropore, feature is to comprise the following steps that：（1）After metal nitrate, triblock copolymer P123 and citric acid are dissolved respectively, citric acid solution is added in nitrate solution, then ethylene glycol is added, stirring 2 hours, triblock copolymer P123 solution is added in nitrate solution again until final total metal salt solubility is 0.4moL/L, is stirred at room temperature 12 hours and obtains precursor solution；（2）Biomass material is added in precursor solution, in 15 40 DEG C of temperature, impregnates 13 days, removes filtrate；Filter residue is placed in drying box, after 50 80 DEG C are dried 24 hours, 600 700 DEG C are warming up to 12 DEG C/min speed in Muffle furnace, 35 hours is incubated, is cooled to room temperature, obtains product, advantage is that have higher specific surface area and porosity.
Description
Technical field
The present invention relates to a kind of perovskite oxide material preparation field, more particularly, to a kind of foramen magnum-mesoporous perovskite
The preparation method of oxide.
Background technology
Perofskite type oxide（ABO3）Great concern is caused due to its unique physicochemical properties, it is extensive
Applied to gas sensor, tail-gas catalyst, battery, electronics and magnetic material etc..Foramen magnum-mesoporous perovskite material possesses two kinds
Type pore structure, additionally include different scale pore structure at the same level, different pore structures is combined, not only with single-stage hole
The excellent properties of material, and with big specific surface area, flourishing multistage pore structure and multi-stage porous synergy, make it
Efficiency of transmission is high, permeance property is good, catalytic performance is good, is better than other single pore structure calcium so as to have in each application field
The characteristic of titanium ore material.
At present based on double-template method, the B of CN 101905903 disclose one kind with poly- first for the preparation of foramen magnum-mesoporous material
Base methyl acrylate (PMMA) microballoon is hard template, 1B or triblock copolymer P123（Full name be PEO-
PPOX-PEO triblock copolymer, its molecular formula are:PEO-PPO-PEO）It is prepared for for soft template template
Foramen magnum-mesoporous LaMnO3 perovskite oxides, wherein the biological template using PMMA to form three-dimensional macropore, 1B and P123
To promote to form mesoporous soft template on the hole wall of macropore.CN 105709740 discloses one kind with polystyrene（PS）It is micro-
Ball and surfactant F127 are that template is successfully prepared the ferrosilicon composite with foramen magnum-mesoporous structure, these macropore-Jie
Pore structure transmission reactant is quick and has special forbidden photon band, therefore the material has good degraded effect to organic dyestuff
Fruit.The A of patent CN 101323504 are disclosed with polystyrene（PS）Glue crystalline substance array and block polymer（P123）It is prepared by double-template
The titanium deoxid film with foramen magnum-mesoporous structure is gone out, the film specific surface area is high and translucency is good, and it is quick to can be applied to dyestuff
Change solar cell.The above method uses chemical template more, and synthesis cycle is long, cost is high, the pollution to environment is larger.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of macropore-Jie with higher specific surface area and porosity
The preparation method of hole perovskite oxide.
Technical scheme is used by the present invention solves above-mentioned technical problem：A kind of foramen magnum-mesoporous perovskite oxide
Preparation method, comprise the following steps that：
（1）It is prepared by precursor solution
After metal nitrate, triblock copolymer P123 and citric acid are dissolved respectively, citric acid solution is added to nitrate
In solution, ethylene glycol is then added, is stirred 2 hours, then triblock copolymer P123 solution is added in nitrate solution directly
It is 0.4moL/L to final total metal salt solubility, is stirred at room temperature 12 hours and obtains precursor solution；
（2）It is prepared by foramen magnum-mesoporous perovskite oxide
Biomass material is added to step（1）In obtained precursor solution, in 15-40 DEG C of temperature, impregnate 1-3 days, remove
Filtrate；Filter residue is placed in drying box, after 50-80 DEG C is dried 24 hours, heated up in Muffle furnace with 1-2 DEG C/min speed
To 600-700 DEG C, 3-5 hours are incubated, room temperature is cooled to, obtains foramen magnum-mesoporous perovskite oxide sample.
The mol ratio of described total metal salt and described triblock copolymer P123 is（150-220）：1；Described is total
The mol ratio of metal salt and described citric acid is（0.5-1）：（1-4）；Mole of described citric acid and described ethylene glycol
Than for（0.4-1）：（1-4）；Described metal nitrate is that any of ferric nitrate, manganese nitrate and cobalt nitrate are pressed with lanthanum nitrate
Metallic element mol ratio 1：1 ratio mixes.
The concentration of nitrate is 0.1-1moL/L in described nitrate solution.
Biomass material is any of shaddock, pollen, ginger bar and broomcorn straw.
Compared with prior art, the advantage of the invention is that：One kind of the invention prepares foramen magnum-mesoporous perovskite with double-template
The method of oxide, it using green, natural, the biomass shaddock of wide material sources, pollen, ginger bar and broomcorn straw is mould that it, which is,
Plate, using biological template as the hard template for forming macropore, P123 adjusts P123 and metal salt as mesoporous soft template is formed
Ratio and concentration, P123 and metal nitrate mixed solution are impregnated into plant template, high-temperature calcination, remove biological template
And P123 templates, foramen magnum-mesoporous perovskite oxide is generated, compared to chemical template method, natural biological template has uniqueness
Fine hiberarchy, by replicate these biological templates structure can effective increasing specific surface area, be advantageous to absorption and
Reactant transmits, and product is had larger specific surface area, flourishing multistage pore structure, makes it in diffusion, mass transfer etc.
The characteristic better than other single pore structure materials is illustrated, improves reactant and perovskite contact area, is advantageous to reaction
The absorption of thing, to accelerating reaction to have great importance.Using multi-stage porous perovskite oxide made of preparation method of the present invention
With cost is low, technique simple economy, environmentally safe.
Brief description of the drawings
Fig. 1 is foramen magnum-mesoporous LaFeO prepared by embodiment 13The X-ray powder diffraction figure of perovskite oxide；
Fig. 2 is foramen magnum-mesoporous LaFeO prepared by embodiment 13Scanning electron microscope (SEM) photograph after perovskite oxide roasting；
Fig. 3 is foramen magnum-mesoporous LaFeO prepared by embodiment 13Mesoporous ESEM on hole wall after perovskite oxide roasting
Figure；
Fig. 4 is foramen magnum-mesoporous LaFeO prepared by embodiment 13The isothermal adsorption of perovskite oxide-desorption curve figure；
Fig. 5 is foramen magnum-mesoporous LaFeO prepared by embodiment 13The graph of pore diameter distribution of perovskite oxide；
Fig. 6 is foramen magnum-mesoporous LaFeO prepared by embodiment 23The X-ray powder diffraction figure of perovskite oxide；
Fig. 7 is foramen magnum-mesoporous LaFeO prepared by embodiment 23Scanning electron microscope (SEM) photograph after perovskite oxide roasting；
Fig. 8 is foramen magnum-mesoporous LaFeO prepared by embodiment 23Mesoporous ESEM on hole wall after perovskite oxide roasting
Figure；
Fig. 9 is foramen magnum-mesoporous LaFeO prepared by embodiment 23Perovskite oxide isothermal adsorption-desorption curve figure；
Figure 10 is foramen magnum-mesoporous LaFeO prepared by embodiment 23The graph of pore diameter distribution of perovskite oxide；
Figure 11 is foramen magnum-mesoporous LaMnO prepared by embodiment 33The X-ray powder diffraction figure of perovskite oxide；
Figure 12 is foramen magnum-mesoporous LaFeO prepared by embodiment 33Scanning electron microscope (SEM) photograph after perovskite oxide roasting；
Figure 13 is foramen magnum-mesoporous LaFeO prepared by embodiment 33Mesoporous scanning electricity on hole wall after perovskite oxide roasting
Mirror figure；
Figure 14 is foramen magnum-mesoporous LaFeO prepared by embodiment 33Perovskite oxide isothermal adsorption-desorption curve figure；
Figure 15 is foramen magnum-mesoporous LaFeO prepared by embodiment 33The graph of pore diameter distribution of perovskite oxide；
Figure 16 is foramen magnum-mesoporous LaMnO prepared by embodiment 43The X-ray powder diffraction figure of perovskite oxide；
Figure 17 is foramen magnum-mesoporous LaFeO prepared by embodiment 43Scanning electron microscope (SEM) photograph after perovskite oxide roasting；
Figure 18 is foramen magnum-mesoporous LaFeO prepared by embodiment 43Mesoporous scanning electricity on hole wall after perovskite oxide roasting
Mirror figure；
Figure 19 is foramen magnum-mesoporous LaFeO prepared by embodiment 43Perovskite oxide isothermal adsorption-desorption curve figure；
Figure 20 is foramen magnum-mesoporous LaFeO prepared by embodiment 43The graph of pore diameter distribution of perovskite oxide.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
It is D8 Focus type powder x-ray diffractions that the present invention, which surveys the instrument of thing mutually,（German Bruker companies）, observation
Pattern be Hitachi, Ltd's production SU-70 electron scanning Electronic Speculum, by the equipment of ASAP 2020 of U.S. Mike carry out nitrogen inhale it is de-
Attached test.Medicine used in the present invention is all analysis level, purchased from Chemical Reagent Co., Ltd., Sinopharm Group and Aladdin reagent（On
Sea）Co., Ltd.
Embodiment 1
A kind of preparation method of foramen magnum-mesoporous perovskite oxide, is comprised the following steps that：
（1）It is prepared by precursor solution
A. according to LaFeO3Middle metallic element mol ratio is 1：1 ratio, weigh 14.5440 grams of Fe (NO3)3·9H2O（Traditional Chinese medicines）
With 15.5884 grams of La (NO3)3·6H2O（Aladdin）Be dissolved in 50mL distilled water stir it is molten to being completely dissolved to obtain nitrate
Liquid；
B. it is 170 by total metal salt and P123 mol ratios：1 ratio, weigh 2.4565 grams of P123 and be dissolved in 20mL distilled water, stir
Mix to dissolving and obtain P123 solution；
C. it is 1 by total metal salt and citric acid mol ratio：1 ratio, weigh appropriate citric acid (AR) and be dissolved in 20mL distilled water
In obtain citric acid solution；
D. citric acid solution is added in nitrate solution, then adds 2.68 grams of ethylene glycol, stirred 2 hours, afterwards will
P123 solution is added in nitrate solution（Final metal salt solubility is 0.4moL/L）It is stirred at room temperature 12 hours before obtaining
Drive liquid solution；
（2）It is prepared by foramen magnum-mesoporous perovskite oxide
A. by fresh grapefruit skin（Official small stream shaddock）Middle pericarp be cut into thin block, water-wash away the impurity on surface, 60 DEG C of drying with distillation
It is standby；
B. 5 grams of pomelo peels are added to step（1）In obtained precursor solution, in 28 DEG C of temperature, impregnate 2 days, remove filtrate；
Filter residue is placed in drying box, after 60 DEG C are dried 24 hours, 600 DEG C are raised to 2 DEG C/min speed in Muffle furnace, is protected
Temperature 4 hours, is cooled to room temperature, obtains foramen magnum-mesoporous perovskite oxide sample.
Perovskite manufactured in the present embodiment is pure phase as shown in Figure 1, and its Perovskite Phase is oblique square structure, and standard card
No. 37-1493 is consistent, and does not form other oxides.Average grain size is 21.72 nanometers.
Foramen magnum-mesoporous perovskite oxide material average pore size after being calcined as shown in Figure 2 is 100-200um, and Fig. 3 is hole
What is formed on wall is mesoporous, its a diameter of 10-50nm.
From Fig. 4 nitrogen adsorption desorption test results, the specific surface area of the porous perovskite of the present embodiment is 23m2/ g, it is average
Aperture is 21 nm, and average pore sizes are 0.098 cm3/ g, from hysteresis loop it can be seen that there is foramen magnum-mesoporous deposit in perovskite
.Fig. 5 is the graph of pore diameter distribution of the porous perovskite of the present embodiment, and hole integrated distribution is in 2nm, 3 nm and 16nm.
Embodiment 2
A kind of preparation method of foramen magnum-mesoporous perovskite oxide, is comprised the following steps that：
（1）It is prepared by precursor solution
A. according to LaFeO3Middle metallic element mol ratio is 1：1 ratio, weigh 14.5440 grams of Fe (NO3)3·9H2O（Traditional Chinese medicines）
With 15.5884 grams of La (NO3)3·6H2O（Aladdin）Be dissolved in 50mL distilled water stir it is molten to being completely dissolved to obtain nitrate
Liquid；
B. it is 170 by total metal salt and P123 mol ratios：1 ratio, weigh 2.4565 grams of P123 and be dissolved in 20mL distilled water, stir
Mix to dissolving and obtain P123 solution；
C. it is 1 by total metal salt and citric acid mol ratio：1 ratio, weigh appropriate citric acid (AR) and be dissolved in 20mL distilled water
In obtain citric acid solution；
D. citric acid solution is added in nitrate solution, then adds 2.68 grams of ethylene glycol, stirred 2 hours, afterwards will
P123 solution is added in nitrate solution（Final metal salt solubility is 0.4moL/L）It is stirred at room temperature 12 hours before obtaining
Drive liquid solution；
（2）It is prepared by foramen magnum-mesoporous perovskite oxide
A. after pollen being washed with water into surface impurity, pollen impregnates 3 times in ethanol, 12 hours every time, removes pollen face grease
Class, 60 DEG C are dried for standby；
B. 5 grams of pollen are added to step（1）In obtained precursor solution, in 15 DEG C of temperature, impregnate 3 days, remove filtrate；Will
Filter residue is placed in drying box, and after 50 DEG C are dried 24 hours, 600 DEG C are raised to 1.5 DEG C/min speed in Muffle furnace, is protected
Temperature 4 hours, is cooled to room temperature, obtains foramen magnum-mesoporous perovskite oxide sample.
Perovskite manufactured in the present embodiment is pure phase as shown in Figure 6, and its Perovskite Phase is oblique square structure, with PDF standard cards
Piece No. 37-1493 are consistent, and do not form other oxides.
As shown in Figure 7, the foramen magnum-mesoporous perovskite oxide material after roasting replicates the pattern of pollen, diameter about 15
Um appearances cover network structure, and mesh size is 0.5-1 um, Fig. 8 be formed on hole wall it is small mesoporous.
From Fig. 9 nitrogen adsorption desorption test results, the specific surface area of the porous perovskite of the present embodiment is 30 m2/ g, put down
Equal aperture is 16.6 nm, and average pore sizes are 0.11 cm3/ g, from hysteresis loop it can be seen that having in perovskite foramen magnum-mesoporous
In the presence of.Figure 10 is the graph of pore diameter distribution of the porous perovskite of the present embodiment, and hole integrated distribution is in 2nm and 16nm.
Embodiment 3
A kind of preparation method of foramen magnum-mesoporous perovskite oxide, is comprised the following steps that：
（1）It is prepared by precursor solution
A. according to LaMnO3Middle metallic element mol ratio is 1：1 ratio, weigh 12.8844 grams of Mn (NO3)2（Aladdin）With
15.5884 gram La (NO3)3·6H2O（Aladdin）It is dissolved in 50mL distilled water and stirs to being completely dissolved to obtain nitrate solution；
B. it is 170 by total metal salt and P123 mol ratios：1 ratio, weigh 2.4565 grams of P123 and be dissolved in 20mL distilled water, stir
Mix to dissolving and obtain P123 solution；
C. it is 1 by total metal salt and citric acid mol ratio：1 ratio, weigh appropriate citric acid (AR) and be dissolved in 20mL distilled water
In obtain citric acid solution；
D. citric acid solution is added in nitrate solution, then adds 2.68 grams of ethylene glycol, stirred 2 hours, afterwards will
P123 solution is added in nitrate solution（Final metal salt solubility is 0.4moL/L）It is stirred at room temperature 12 hours before obtaining
Drive liquid solution；
（2）It is prepared by foramen magnum-mesoporous perovskite oxide
A. by ginger bar be cut into diameter be about 1 centimetre, high 1 centimetre of cylinder, wash away surface impurity with distilled water, be placed in baking oven
In, in 60 DEG C, dry 24 hours, it is standby；
B. 5 grams of ginger bars are added to step（1）In obtained precursor solution, in 40 DEG C of temperature, impregnate 1 day, remove filtrate；Will
Filter residue is placed in drying box, after 70 DEG C are dried 24 hours, is raised to 700 DEG C in Muffle furnace with 1 DEG C/min speed, insulation 3
Hour, room temperature is cooled to, obtains foramen magnum-mesoporous perovskite oxide sample.
Perovskite manufactured in the present embodiment is pure phase as shown in Figure 11, similar with Emission in Cubic, with standard card No. 75-
0440 is consistent, and does not form other oxides.
As shown in Figure 12, the foramen magnum-mesoporous perovskite oxide material after roasting replicates the pattern of ginger bar, and macropore is
100-400nm, pore diameter range are wider.Figure 13 is mesoporous, the pore diameter range on foramen magnum-mesoporous perovskite oxide material hole wall
For 10-50nm.
From Figure 14 nitrogen adsorption desorption test results, the specific surface area of the porous perovskite of the present embodiment is 30 m2/ g, put down
Equal aperture is 24.6 nm, and average pore sizes are 0.129 cm3/ g, from hysteresis loop it can be seen that having in perovskite foramen magnum-mesoporous
In the presence of.Figure 15 is the graph of pore diameter distribution of the porous perovskite of the present embodiment, and hole integrated distribution is in 2nm and 16nm.
Embodiment 4
（1）It is prepared by precursor solution
A. according to LaCoO3Middle metallic element mol ratio is 1：1 ratio, weigh 10.4771 grams of Co (NO3)2·6H2O（Traditional Chinese medicines）
With 15.5884 grams of La (NO3)3·6H2O（Aladdin）Be dissolved in 50mL distilled water stir it is molten to being completely dissolved to obtain nitrate
Liquid；
B. it is 170 by total metal salt and P123 mol ratios：1 ratio, weigh 2.4565 grams of P123 and be dissolved in 20mL distilled water, stir
Mix to dissolving and obtain P123 solution；
C. it is 1 by total metal salt and citric acid mol ratio：1 ratio, weigh appropriate citric acid (AR) and be dissolved in 20mL distilled water
In obtain citric acid solution；
D. citric acid solution is added in nitrate solution, then adds 2.68 grams of ethylene glycol, stirred 2 hours, afterwards will
P123 solution is added in nitrate solution（Final metal salt solubility is 0.4moL/L）It is stirred at room temperature 12 hours before obtaining
Drive liquid solution；
（2）It is prepared by foramen magnum-mesoporous perovskite oxide
A. by broomcorn straw be cut into diameter be about 1 centimetre, high 1 centimetre of cylinder, wash away surface impurity with distilled water, be placed in baking
In case, dried 24 hours in 60 DEG C, it is standby；
B. 5 grams of broomcorn straws are added to step（1）In obtained precursor solution, in 25 DEG C of temperature, impregnate 2 days, remove filter
Liquid；Filter residue is placed in drying box, after 80 DEG C are dried 24 hours, 650 DEG C are raised to 2 DEG C/min speed in Muffle furnace,
Insulation 4 hours, is cooled to room temperature, that is, obtains foramen magnum-mesoporous perovskite oxide sample.
Perovskite manufactured in the present embodiment is pure phase as shown in Figure 16, similar with rhombus Perovskite Phase, with standard card
No.48-0123 is consistent, and does not form other oxides.
As shown in Figure 17, foramen magnum-mesoporous perovskite oxide material manufactured in the present embodiment replicates the shape of broomcorn straw
Looks, macropore diameter scope are 5 nm-5 um, and pore size distribution range is wider.Figure 18 is foramen magnum-mesoporous perovskite oxide material
Mesoporous on hole wall, its pore diameter range is 10-50 nm.
From Figure 19 nitrogen adsorption desorption test results, the specific surface area of the porous perovskite of the present embodiment is 30 m2/ g, put down
Equal aperture is 24.6 nm, and average pore sizes are 0.129 cm3/ g, it can be seen that having in perovskite foramen magnum-mesoporous from hysteresis loop
Presence, Figure 20 be the present embodiment porous perovskite graph of pore diameter distribution, hole integrated distribution is in 2 nm and 16 nm.
In addition to the implementation, the mol ratio of total metal salt and triblock copolymer P123 can be 150：1、160：1、
180：1、190：1、200:1、210:1 and 220：1, can also be（150-220）：Arbitrary value in 1；Total metal salt and lemon
It can be 0.5 that the mol ratio of acid, which is,：1、1：4、0.8：2 and 0.5：4, can also be（0.5-1）：（1-4）Interior arbitrary value；Lemon
The mol ratio of lemon acid and ethylene glycol is 0.4：1、0.6：2 and 0.4：4, can also be（0.4-1）：（1-4）Interior arbitrary value.Nitre
The concentration of nitrate can also be the arbitrary value in 0.1-1moL/L in acid salt solution.
Described above is not limitation of the present invention, and the present invention is also not limited to the example above.The art it is common
Technical staff is in the essential scope of the present invention, the variations, modifications, additions or substitutions made, should also belong to the protection of the present invention
Scope.
Claims (4)
1. a kind of preparation method of foramen magnum-mesoporous perovskite oxide, it is characterised in that comprise the following steps that：
（1）It is prepared by precursor solution
After metal nitrate, triblock copolymer P123 and citric acid are dissolved respectively, citric acid solution is added to nitrate
In solution, ethylene glycol is then added, is stirred 2 hours, then triblock copolymer P123 solution is added in nitrate solution directly
It is 0.4moL/L to final total metal salt solubility, is stirred at room temperature 12 hours and obtains precursor solution；
（2）It is prepared by foramen magnum-mesoporous perovskite oxide
Biomass material is added to step（1）In obtained precursor solution, in 15-40 DEG C of temperature, impregnate 1-3 days, remove
Filtrate；Filter residue is placed in drying box, after 50-80 DEG C is dried 24 hours, heated up in Muffle furnace with 1-2 DEG C/min speed
To 600-700 DEG C, 3-5 hours are incubated, room temperature is cooled to, obtains foramen magnum-mesoporous perovskite oxide sample.
A kind of 2. preparation methods of foramen magnum-mesoporous perovskite oxide of according to claim 1, it is characterised in that：It is described
The mol ratio of total metal salt and described triblock copolymer P123 be（150-220）：1；Described total metal salt with it is described
The mol ratio of citric acid be（0.5-1）：（1-4）；The mol ratio of described citric acid and described ethylene glycol is（0.4-1）：
（1-4）；Described metal nitrate is that any of ferric nitrate, manganese nitrate and cobalt nitrate press metallic element mole with lanthanum nitrate
Than 1：1 ratio mixes.
A kind of 3. preparation methods of foramen magnum-mesoporous perovskite oxide of according to claim 2, it is characterised in that：It is described
Nitrate solution in the concentration of nitrate be 0.1-1moL/L.
4. a kind of preparation methods of foramen magnum-mesoporous perovskite oxide of according to any one of claim 1-3, it is special
Sign is：Biomass material is any of shaddock, pollen, ginger bar and broomcorn straw.
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| CN107055630A (en) * | 2017-03-09 | 2017-08-18 | 南京工业大学 | The perovskite material 3DOM SmCoO of three-dimensional ordered macroporous structure3And its preparation method and application |
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| CN101323504A (en) * | 2008-06-13 | 2008-12-17 | 天津大学 | Preparation of macroporous-mesoporous nanocrystalline titania film |
| CN101905903A (en) * | 2010-07-30 | 2010-12-08 | 北京工业大学 | Manufacturing method of dual-template of three-dimensionally ordered macroporous lanthanum manganate with mesoporous wall of hole |
| CN107055630A (en) * | 2017-03-09 | 2017-08-18 | 南京工业大学 | The perovskite material 3DOM SmCoO of three-dimensional ordered macroporous structure3And its preparation method and application |
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| CN108380203A (en) * | 2018-02-12 | 2018-08-10 | 宁波大学 | A kind of hollow nucleocapsid spherical shape LaMnO of mesoporous wall3Perovskite catalyst and preparation method thereof |
| CN108380203B (en) * | 2018-02-12 | 2020-10-20 | 宁波大学 | Mesoporous wall hollow core-shell spherical LaMnO3Perovskite catalyst and preparation method thereof |
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| CN107673411B (en) | 2019-05-28 |
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